Those games I bought and loved:
FF7, FF8, FF9.
Parasite Eve.
Gran Turismo 1/2.
Silent Hill (this game was one of the few that scared me).
Resident Evil 1-3 (2 is the best RE imo).
Diablo 1 (its addicting as hell, especially 2 Player mode on one screen).
MGS ofcourse which you already have.
Tomb Raider 1 and 2 (2 is the best one)
Tekken 3 (best one).
Dead or Alive (Bouncing tits in 32 bit and atleast as good as Tekken 3 imo)
And Command and Conquer Red Alert in 2 player mode SP wouldn't be much fun today (Needs 2 PS1, 2 TV ,1 Cable but it was totally worth it back then )
With those games I had the best time.
Edit: Forgot certainly a few games, like Alundra, you should totally get that.