Danny Glover grabbed the opener after 53 minutes before Laurence Wilson and Glenn Rule saw red within two minutes.
Simon Richman scored his second goal in three days before James Lawrie netted the goal of the game in the 89th minute.
In a scrappy opening it was the visitors who were unfortunate not to be ahead in the 13th minute when Ritchie Partridge's deft chip clipped the top of Joe Anyon's crossbar.
Steve Thompson responded minutes later for Vale but could only plant his close range header into the arms of John Danby.
And Chester were beginning to stamp their authority on the game with Ryan Lowe and Wilson orchestrating most of the play.
Vale, who began the game two points and a place above their opponents, offered very little going forward and the half time whistle was greeted with boos by disgruntled fans.
The home side responded positively to the criticism and almost shocked their opponents in the 52nd minute with Danby having to deny Richman from point-blank range.
Just seven minutes later a mix-up between Danby and Kevin Roberts allowed Danny Glover to nip in for his second goal of the season.
Chester then gave their hosts a double helping hand within two minutes when Wilson saw red on 70 minutes after a lunge on Thompson and he was soon joined in the dressing room by Rule.
Substitute Robert Taylor bundled in at the far post in the 74th minute for the second and fellow sub Lawrie curled home the third to seal an emphatic win.