I've played countless hours on all the games of this fantastic series.
Smash 64 was the first I grew up with. While it still holds today and is great fun, it feels lacking in content and in mechanics compared to its successors. No side B moves, no Final Smashes, no wall jumps, etc. Nevertheless, it introduced me to Samus, Capt. Falcon, and Ness. Heck the single player was bad back in the day, just more expanded in the sequels.
Melee was probably my most played game during the sixth gen. The competitive community, though, has kinda turned me off a bit recently with so much in favor of Melee. Yes it's a helluva game and it's fast, but not everyone can master the mechanics and expect to compete effectively, especially those with less time on their hands...Anyways, incredible experience with a solid (not the greatest) Adventure mode, great characters (though unbalanced compared to 4), and unique stages and music that I wish came back to 4.
Brawl was incredible. Paving the way for 3rd party characters and creating the dream matchup of Mario and Sonic. SSE was pretty good even if it was repetitive, Boss Battles were fun, the other modes were fun. Though I never tried online because I wasn't really sure how it worked at the time so I missed out. Still great game despite being a little slower than Melee for some (didn't bother me too much).
Smash 4 was, and still is, great. Whenever I'm undecided on what game I want to play, I go back to Smash 4. Solid new modes like Smash Run, 8-player Smash (yes, even while alone since it's so chaotic), online (which does work well for me for the most part), plethora of music, stages, collectibles, and, of course, probably the greatest crossover roster ever, let alone video games. We will probably never see Mega Man, Pac-Man, Ryu, Sonic, Mario, Cloud, and Bayonetta in the same game again unless they can come back for the next game along with the new and old generation of Nintendo characters already in the game as well.
Hard to choose, but I'll pick 4 over the rest, even though I would gladly come back to those games when asked. The roster alone makes it for me, as well as a solid online, the collectibles, stages, and the potential for 8-player Smash, which is fun to play (even while alone) and to watch (check YoVideoGames and their hysterical 8-player sessions.