Not to promote another site, but if you are really interested in corporate aviation, *************.com is a good place to start networking. It's worth the $10/year, and there are a LOT more corporate/frax guys there than on these forums. (I'd say that site is for 91/135 flying that this is for 121 flying).

The big thing for anybody wanting to make the jump is to network network network. Most jobs are right place/right time or through inside connections. Just because you work for an airline doesn't mean that you can't find a way to get to know local operators...

Local safety seminars and regional/national aviation conferences are good places to start. Consider trying to attend an event like the Annual Bombardier/NBAA Safety Standown or the NBAA National Convention.