The opening day of the £500,000 event saw 32 first round ties played across one marathon session of darts, and the tournament was blown wide open as four of the top eight seeds crashed out at Butlin's Minehead Resort.
World number one Price was sent packing by Ryan Joyce after squandering three match darts in a dramatic last-leg affair on the Main Stage.
Joyce - who led 3-0 at one stage - missed three match darts of his own before returning to prevail via double eight, and he now takes on a resurgent Jermaine Wattimena, who eased past Brendan Dolan in his opener.
Elsewhere, newly crowned Grand Slam of Darts champion Michael Smith suffered a shock opening round exit against Ritchie Edhouse, who defied a 12-point disparity in the averages to secure one of the biggest wins of his career.
Smith - who averaged 98 - led 5-3 before Edhouse reeled off three consecutive legs to triumph, and the Enfield ace will face Dimitri Van den Bergh for a place in round three after the Belgian came through a gruelling tussle against Martin Lukeman.
German youngster Ricardo Pietreczko caused a major upset on his TV debut, edging out top seed Damon Heta in a deciding-leg tie to set up a showdown against Callan Rydz, who overcame Madars Razma in similar fashion.
Elsewhere, third seed Nathan Aspinall paid the price for a profligate display as he succumbed 6-4 to Martijn Kleermaker, and the Dutchman will play Matt Campbell for a place in the last 16, after the clinical Canadian accounted for Steve Beaton.
However, six-time champion Michael van Gerwen avoided the same fate as his main rivals, reeling off three straight legs to come through a high-quality tussle against Suffolk's Ryan Meikle.
Van Gerwen - chasing a record-extending seventh title at this event - closed out a 6-3 victory to create a tie against Cameron Menzies, who impressed in defeating Josh Rock by the same scoreline.
"It's only a short format so you have to play your best if you want to win games," reflected Van Gerwen, who averaged 102 and converted six of his 11 attempts at double.
"Cameron Menzies is a good player and when he's on it, he can do some real damage, but I don't care who I play, you have to beat them all to win this tournament."
Second seed Luke Humphries also avoided an early exit, producing a professional display in his 6-3 success against Nathan Rafferty, and Mike De Decker now awaits, after the Belgian toppled Jim Williams in a contest featuring nine 180s.
Danny Noppert produced the performance of the opening day in Minehead, converting stunning 140 and 164 finishes in consecutive legs to complete a 6-1 demolition of Simon Whitlock.
Noppert - making his first Minehead appearance since a UK Open triumph in March - averaged 106 and defied five 180s from Whitlock to book a meeting with ten-time TV title winner James Wade, who swept aside a below-par Mensur Suljovic.
European Champion Ross Smith produced a flawless display of finishing to dispatch debutant Gian van Veen, converting all six of his attempts at double to set up a mouth-watering showdown against Jonny Clayton - a whitewash winner against John O'Shea.
Former World Champions Rob Cross and Gary Anderson will collide in another tasty tussle, after both men produced battling displays in wins over Kevin Doets and Gabriel Clemens respectively.
Fourth seed Dirk van Duijvenbode recovered from 4-2 down to defeat Mickey Mansell in a last-leg decider, and his reward is a second round clash against 2018 winner Daryl Gurney, who ran out a comfortable 6-3 winner against Keegan Brown.
Masters champion Joe Cullen reeled off four straight legs to ease past Rowby-John Rodriguez and set up a second round tussle against Kim Huybrechts, who posted a 101 average in his 6-4 success against Grand Slam semi-finalist Raymond van Barneveld.
Former finalist Dave Chisnall returned to winning ways on the big stage, defying a spirited rally from Niels Zonneveld to move through to an encounter against Scott Williams, who dumped out Grand Slam quarter-finalist Alan Soutar earlier in the day.
Jose De Sousa reeled off five consecutive legs to record an emphatic 6-2 win over Dutch debutant Danny Jansen, and the Portuguese ace will face Krzysztof Ratajski in round two, after Poland's number one saw off William O'Connor.
UK Open semi-finalist Keane Barry continued his love affair with Minehead to dump out two-time finalist Adrian Lewis, and the Irishman will return to play Andrew Gilding, who posted a ton-plus average in his 6-2 success against Ricky Evans.
Martin Schindler also averaged in three figures in his 6-4 victory over Vincent van der Voort, fending off the Dutchman's late rally to create a last 32 tie against Chris Dobey, who breezed past Geert Nentjes 6-1 to advance.
Meanwhile, last year's finalist Ryan Searle completed an impressive comeback win over two-time runner-up Mervyn King on Stage Two, and he will play Jamie Hughes on Saturday afternoon, after the Tipton star claimed the scalp of Stephen Bunting.
The battle to claim the last piece of silverware before the World Championship continues on Saturday, with 16 second round ties played across the Main Stage and Stage Two in the afternoon.
Round Two winners will then return in the evening session to compete for a place in the quarter-finals, with eight games played across both stages.
2022 Cazoo Players Championship Finals
Friday November 25
Rob Cross 6-3 Kevin Doets
Joe Cullen 6-2 Rowby-John Rodriguez
Ricardo Pietreczko 6-5 Damon Heta
James Wade 6-2 Mensur Suljovic
Cameron Menzies 6-3 Josh Rock
Ross Smith 6-2 Gian van Veen
Martijn Kleermaker 6-4 Nathan Aspinall
Dimitri Van den Bergh 6-5 Martin Lukeman
Danny Noppert 6-1 Simon Whitlock
Ritchie Edhouse 6-5 Michael Smith
Ryan Joyce 6-5 Gerwyn Price
Kim Huybrechts 6-4 Raymond van Barneveld
Michael van Gerwen 6-3 Ryan Meikle
Luke Humphries 6-3 Nathan Rafferty
Dave Chisnall 6-3 Niels Zonneveld
Andrew Gilding 6-2 Ricky Evans
Callan Rydz 6-5 Madars Razma
Daryl Gurney 6-3 Keegan Brown
Scott Williams 6-4 Alan Soutar
Jermaine Wattimena 6-3 Brendan Dolan
Mike De Decker 6-4 Jim Williams
Krzysztof Ratajski 6-4 William O'Connor
Keane Barry 6-4 Adrian Lewis
Jose de Sousa 6-2 Danny Jansen
Dirk van Duijvenbode 6-5 Mickey Mansell
Ryan Searle 6-4 Mervyn King
Jamie Hughes 6-4 Stephen Bunting
Chris Dobey 6-1 Geert Nentjes
Martin Schindler 6-4 Vincent van der Voort
Jonny Clayton 6-0 John O'Shea
Matt Campbell 6-3 Steve Beaton
Gary Anderson 6-4 Gabriel Clemens
Saturday November 26
Afternoon Session (1245-1700 GMT)
Dirk van Duijvenbode v Daryl Gurney
Ritchie Edhouse v Dimitri Van den Bergh
Rob Cross v Gary Anderson
Ross Smith v Jonny Clayton
Luke Humphries v Mike De Decker
Danny Noppert v James Wade
Cameron Menzies v Michael van Gerwen
Joe Cullen v Kim Huybrechts
Ricardo Pietreczko v Callan Rydz
Andrew Gilding v Keane Barry
Krzysztof Ratajski v Jose De Sousa
Martin Schindler v Chris Dobey
Ryan Joyce v Jermaine Wattimena
Martijn Kleermaker v Matt Campbell
Dave Chisnall v Scott Williams
Ryan Searle v Jamie Hughes
Best of 11 legs