No question about it; Piccard.
He had high expectations of his crew to do their best, not have excuses for **** ups and allowed your time off to be yours.
Archer was too busy skipping through time to be effective
Pike became a cripple after serving a few good years. Was a decent man, but not enough experience to leave a good impression. He wrecked a lot of boats.
Lorca was a crazy man. I'd like to finish my career in Starfleet
Georgiou seemed to be a bit of a bitch. Plus, who wants a female captain as first captain?
Old Kirk was busy grabbing them by the Pussy (That's just for you Izzy)
Spock would have been a good Captain I think. There would not be any emotional breakdowns.
Sulu might also have been good, but I am not familiar enough with his full record to be able to judge.
Scotty... did he command a full Starfleet vessel or just a party barge?I got to meet him once at a con. Seemed like a generous and kind man.
April... No idea about his record, had a familiar voice though.
Young Kirk... Volitile, self sacrificial, lost too many boats which he continued doing later in life...
Riker? No. He is a second commander looking for a captain. He does not make good decisions.
Jellico? Seriously? No.
Garrett... Probably not.
Sisko had too much **** going on with the prophets to have time for his crew
Janeway? Gets lost too easily.
Freeman? No idea.