Picard was a thinker, but also a fighter. As a younger man, he'd fought a lot, and would get into trouble. He mellowed with age, but was still capable of taking it to the enemy. But he had a greater capacity for compassion and empathy, which I think made him a more capable leader, and someone who could be trusted to do the right thing.

And I won't deny it... Picard has enormous sex appeal. ?

Picard, hands down.

Focusing only on the original series vs. TNG, when compared with Captain Kirk, one is sometimes tempted to dismiss Jean-Luc Picard as being too cerebral. Notwithstanding Kirk’s fistfights, shoulder rolls and numerous dalliances, I find Picard as the one to emulate. Stabbed through the heart in a bar by Nausicaans, assimilated by the Borg as Locutus, tortured without surrendering to the Cardassians, taken on the Romulans and having had a passionate relationship with fellow anthropologist Vash, one simply cannot accuse Picard of being a dispassionate academic.

Admiral Ackbar.
Or Malcolm Reynolds.
I can't pick one over the other.

I'm a Star Trek fan but I can't say that I really have a favorite captain. Still, I'd say Kirk and Picard are out front, with Janeway a close third. They each brought something different to the shows they were on. Kirk was a fighter, Picard was a thinker, and Janeway was a bit of both.