Okay, so here we go. My top 10 ranking for Captains featured in Star Trek. Note, this includes anyone to serve as a Commanding Officer throughout the series or movies. Ergo, several may be in here you might not count. Remember, this is my opinion, and in no way reflects a definitive list.
10: Kathryn Janeway
Honestly, she only makes the list to avoid Voyager fans not murdering me. I hate Janeway with a passion. She was a mildly unlikable character throughout most of the serious, whom I came to loathe in season six when she punished Tom Paris (My favourite character in Voyager, just saying) for doing exactly what she did in the pilot. That also cemented her as one of the worst Captains we ever saw in my book. Anyway, let's move on.
9: Christopher Pike (Prime)
So, I can't really give him too high a rating, given he only appeared once (twice if you include the original pilot). But the original Star Trek Captain, and second Captain of the Enterprise makes the ninth place in this list. He was very different to Kirk, and had an almost militarised Picard type vibe, which really did work. It's a shame we didn't get to see more of him.
This one is ambiguous. Technically, Worf was the XO of the Defiant. However, he was in command in First Contact, and thus, in my eyes, deserves his spot on this list. He was great in that battle scene with the Borg, and honestly, how many other times have you seen any Starfleet Captain be willing to ram the enemy ship? The only time I can think of is Nemesis where Picard had Troi do it (Did they not learn from Generations not to let her take the helm?!)
7: James T Kirk (Alternate)
The 2009 version of the Starfleet Captain makes number 7. Chris Pine portrays him amazingly (I actually think he's a better actor than Shatner), and he is smart enough to know when to break the rules, just like his prime counterpart. However, he is still the wet behind the ears starting out Captain, so unfortunately, I can't rank him higher.
6: Hikaru Sulu
Who doesn't love Sulu? He's awesome, he's intelligent. It's just a shame we didn't get to see more of him in command of Excelsior. Then again, there are several books if you want that, a few of them having Chekov as his XO!
5: Benjamin Sisko
Sisko was brilliant, and I'd love to put him further up this list. However, I can't do that, due to the remaining characters. Instead, I will say this; he was at the front line for the entire Dominion war, he was a religious icon, and he turned out to be half god! That's awesome, and on top of that, he helped design the Defiant! Sounds deserving of this spot to me.
4: Spock (Prime)
So, we only saw Spock in this role in Wrath of Khan, and only for part of it. However, it was great to see him finally take the centre seat. However, when the time came, he handed it over to Kirk, and a good thing too, or we wouldn't have had the best death scene in Star Trek.
3: Jean-Luc Picard
I love Picard. I love his mentality of being a diplomat first, I love how his tactics work, and I love his general Command style. However, he is a lot less willing to break the rules than the top two on this list, which leaves him in trouble a few times. That being said, how many can claim to have Commanded both the Enterprise and a Borg Cube?
2: William T Riker
Yes, he was a Captain. Both post Nemesis, or if you want an example of him in command in canon, Best of Both Worlds. Honestly, I agree with Q in his first appearance on Voyager, Riker should've had that command. He cements his place in this position with three words; "Mister Worf. Fire."
1. James T Kirk (Prime)
Could it be anyone else? Kirk is the quintessential Starfleet Captain. My only gripe? He shouldn't have been killed in Generations. He should've survived and been made the Starfleet CinC, or even, given the Enterprise! Can you imagine Kirk with Riker as his First Officer?! It'd be the best movie ever!
Honestly, there was a case to be made for him being number 10. However, since I have no reason to rank him above Janeway (besides Scott Bakula) I couldn't do it. However, he was great, and I do love Enterprise.
So, that's the list. Please, feel free to comment with your own opinions, I'd love to hear them :)