I took the "long" way round to the corporate pilot world. Regional FO -> Regional CA -> Left professional flying (6 years - did part time instructing) -> 135 SIC -> 135 PIC -> Corporate PIC

The 135 time was great for learning more about the charter and corporate environment. It's different than 121, but still not difficult just different.

I think going direct it'd be a difficult transition to make, unless you have some experience in that arena already. But passed that, just get used to cleaning and detailing planes. With the way salaries have gone in the regional world, financially it'd likely be a lateral...might make a little more corporate initially, but nothing compared to 121 major salaries...or 121 retirements (as they stand right now)