Having spent a career in corporate aviation with two major flight departments, I can tell you that it is a rewarding experience, with good working conditions and benefits. Corporate pilots are exempt employees - white collar - and are hired the same way executives and other exempt employees is which is through submitting a resume to the HR Department. They will pass it to the aviation department and it will be kept on file until their are openings. There are a lot of good flight departments still around although God only knows what the current economic situation is going to do to aviation in general.
Incidentally, there is no particular background qualifications for corporate aviation. Some departments want only ex-military while some want all-civilian. A furloughed airline pilot is probably not going to be hired because they are looking for longevity when they hire a new pilot, who is usually going to be hired at the entry level regardless of experience. How an applicant is going to fit into the department is more important than type ratings and flight hours. Coca-Cola has had an aviation department for decades and would be a good job.