Chopra sent an early season message to the England selectors with a fine, agressive innings of 163, while in-form Ireland captain Porterfield made his first first-class century for Warwickshire as they put on a mammoth 308-run partnership for the second wicket.
Watch: Warwickshire dominate on day one
Peter Trego had earlier provided the perfect start for MCC after Jim Troughton won the toss and elected to bat, removing Ian Westwood for a duck to leave the county champions 0/1.
The Somerset pair of Trego and Steve Kirby continued to bowl wilfully on a flat pitch, but it wasn't long before Porterfield in particular began to dominate proceedings.
The century partnership was reached before lunch as Chopra also warmed to the task, and the Warwickshire pair continued where they'd left off after the break, with Chopra first to his ton off 165 balls.
Porterfield was dropped on 60 and looked nervous as his century approached, scoring slowly through the 90s, but eventually celebrated his ton with a top-edged sweep for three.
Porterfield on the attack
MCC would have hoped that the twilight period might have caused the batsmen a few worries prior to the tea interval, but there was no such luck.
Indeed, Chopra returned after tea in the mood to dominate, striking two sixes in quick succession, while Porterfield regained his rhythm nicely as the 300 partnership was reached.
Left-arm spinner Simon Kerrigan, part of the winning Lancashire team in this fixture last year, tempted Chopra into one shot too many however, with the opener offering a simple catch to Steve Kirby at mid-off.
There was more success for MCC prior to the close as Porterfield slashed a drive to point off Chris Rushworth, where Kerrigan took a fine catch.
Troughton and young Laurie Evans were watchful in the last 45 minutes of the day, and Warwickshire have an ideal platform to build on for day two.