I'd think the only way you could walk in as a captain, even at a start-up, would be if you had turbine captain experience, and more likely 121 at that. Sitting as a lear FO for 6 years isn't going to do it. In fact, it's probably going to work against you - hiring in as a captain, that is.

You can't expect to skip a rung on the ladder just because you chose to sit where you're at for as long as you did.