Well, PS1 helped usher in a new licensing & distribution model more beneficial for third-parties, but the N64 made analog controls a mainstream standard and also pushed 4-player local multiplayer.
So if you separate the console from the games, just speaking of the consoles themselves, the N64 was more innovative. But in terms of the software library that would eventually come about, especially in terms of game originality (not necessarily if the game revolutionized huge parts of the industry), then IMO the PS1 takes that easily.
Like right now I'm playing Moon RPG Remix (yes, the abandoned translation. Pretty much fully translated for the most part tho); you won't really find anything with that type of originality on the N64. PS1 is also where genres like survival-horror and JRPGs saw their biggest innovations in.
So for strictly the hardware itself, it's N64. For the games, it's PS1.
Err, I think you got it wrong. Its quite the opposite, playstation haves way more games, but the amount of good ones it's actually lower than the N64's.
No it's not; N64 definitely has more of the absolute industry-defining standouts (Mario 64 and Ocarina of Time, primarily; also arguably Smash Bros. and Mario Kart 64), but there's no way in hell it has more "good" games than the PS1 or even the Saturn, statistically speaking.
Both of those other systems have so many more games that, going by statistical averages, they're bound to have more games of quality on them than the N64. It's like how the MegaDrive may have some great JRPGs, but the SFC simply has a lot more of them due to having so many more in general, so it's bound to have more good JRPGs than MegaDrive.
You could tally up game count averages for any given score bracket and perhaps outside of the very top of those score brackets, PS1 (and to a lesser extent, Saturn) are going to outdo the N64 in terms of number of games in those brackets. In some cases, vastly so.