Archer and Janeway second, 'cause they had to do the job without any kind of backup. heck, Archer had to figure it out on his own.
Sisko would be next, 'cause he had to deal with a war, and Picard would be last 'cause he basically just patrolled a dull and bloated empire.
Pike was pretty cool too, just didn't see enough of him. I still think they shoulda had Ray Liotta play him.