I've never had more fun with couch multiplayer than I did with the N64: 007, World is Not Enough, Battletanx, Perfect Dark, Mario Kart 64, Diddy Kong Racing, Wave Race, Duke Nukem, Mario Party....there are probably many more that I'm forgetting. That system gave (and still gives) me so much joy with its multiplayer.
But I'd probably still give the "quality" label to PS1. There were just so many more games to choose from in the end that no matter who you were, there was a game for you. Absolutely iconic games that defined its generation.
Personal Enjoyment: N64
Higher quality console with more games: PS1. (Probably the winner)