I think it comes down to a few things, Pilot skill and competence, attitude, willingness to adapt to a new enviroment. Back ground experience will get you an interview but personality will get you a corporate job.
My background was primarilly military and let me tell you this, no one understands customer service better.
When I flew attack my "customer" was the ground commander and his troops, and if I couldn't put steel on target I had a very unhappy customer, perhaps more so than the charter guy who stocked coke instead of pepsi.
After flying attack I moved to VIP flight flying the Generals and thier staffers. Again I needed a full understanding of being on time and anticipating my "customer's" needs. For all intents and purposes VIP flying is corporate flying with a military uniform on. I had a corporate job offer on the table for 2yrs before I left active duty to accept my first full time corporate gig.
It depends a lot on your background, my flying in multiple crewed aircraft and the flight profiles lended itself very well into corporate flying. If a pilot is coming out of single seat fighters it may be more difficult to adapt to the shared responsabilities in a modern two crew aircraft, or for that matter the pilot who flew large aircraft and had the luxury of assigned crewmembers to do the extra duties not directly associated with flying the aircraft.
The argument could also be made ( Falcon Capt correct me if I'm wrong ), that furloughed airline pilots are not neccessarily the best choice for corporate flight depts. They are more than qualified to fly the airplanes but some find it beneath them to shlept bags or be willing to alter thier schedules based on the customer's desires.
There is no one correct answer or solution to this career field, there are only things that one can do to make himself a better candidate. The first is get a degree, and I strongly recomend one not in aviation. After that it comes down to experiences and attitude and preparation. Good Luck is when preparation meets opportunity.
Jim