virtua fighter 2 and last bronx are old, but they're some of the best IMO. Both work under XP too, but might require some trickery before they run properly. Being ports from Sega themselves, they're right up there with the Saturn versions in terms of gameplay.
Afaik VF2 has some sort of multiplayer too.... dunno about Last Bronx.
If you need help getting them to run properly, just ask.