How about Jed Bartlett?
Spock
Especially when they stole his brain!
How about Jed Clampett?
Cursing G-d ain’t so smart.
Cool, but not smart. 
I was thinking more along the lines of “Well, gentlemen, one of you is the real Captain Kirk and one of you is the evil shapeshifting Garth, so I’ll just turn my back for a moment…”
Gil Grissom from CSI.
Ah, but he knew Kirk would lose.
Huey Freeman on the Boondocks? There aren’t really typical wacky misunderstanding hijinks on Boondocks and he’s a bit young for romantic relationships, but he does typically see through the BS that others get taken in by. (Like when Jazmine was selling lemonade for Ed Wuncler or when Riley refused to believe that Gangstalicious was gay.)
Very good choice. Ed O’Neil’s character on *Modern Family *might qualify here as well.
The winner, of course, is The Most Interesting Man in the World. He had an awkward moment once, just to see what it felt like.
Kif Kroker.
My vote is for Oscar from The Office. He seems like he just accidentally ended up on a sit-com.
He loses points because he continues to work for Zap Brannigan.
Also, most of the list is just Truth In Television–people really are that stupid.
Let’s see, called the rich babe who had the hots for him for a year and was too nervous to say anything.
No.
Edward Wong Hau Pepulu Tivruskii IV
Master Po from Kung Fu seemed to have his shit together.
Columbo episodes play out pretty much the same if you figure he’s the writer, such that he of course already knows whodunit and is just working to come up with an interesting way of demonstrating it.
I’m going to go with Booth from Bones. He seems to have his act together.
Most characters on the wire.
Al Swearengen (deadwood)
Larry David (Curb Your Enthusiasm)
Sarah Jane Anastasia Silverman (the sarah silverman program)
Oh, and fucking captain picard
The first that came into my head was Edmund Blackadder, but I haven’t watched it for a while so I could be missing something obvious. when he got into blunders, it was usually because some numbnuts gave him the wrong information.