Of course some people can hack it and others can't. Some pilots should never be a captain....ever! I've seen others that are fantastic 2000 hour captains....but it's rare.

And yes...I do think that corp pilots flying small jets and turboprops around are going to have a much easier time at an airline than a fresh recruit straight out of a piston twin trainer. The thing is, the economies of the business make the airlines the entry level jobs. Most corporate flight departments can't take low time pilots, especially as captains, due to the much higher insurance costs.