I've always found the grumpiest captains to ask for the jumpseat from are the younger regional lifers- guys in their later 40's or early 50's or so that have gotten somewhat senior for whatever reason and can't viably move on to a real career job, yet aren't happy with where they are at.
Some personal favorites have been in ASA CRJ-700s... yowza! (to be fair I've run into some real characters at least once at every carrier I've routinely jumped on- Pinnacle, ASA, comair, shuttle america, Delta, and Northwest)
Me- "Hello sir, my name is xxx, I work at Delta, may I catch a ride with you guys today?" (all the usual credentials extended out)
CA- "You aren't going to be riding up front are you?"
Me- "Huh.. uh.... maybe? It could go either way right now"
CA- "I hope not." (shoves credentials back at me)
*crickets
Me- "I appreciate the ride...."
Some people wonder why they can't get hired elsewhere....