I would probably classify myself as one of those low time guys and I am currently working for a Fortune 300 company. In all honestly I don't think that I would have ever been considered for the position if it had not been for personal recommendations one of which came from my previous chief pilot. I was in a unique situation, I was working for a company that was eliminating their flight department.
Althought I didn't have a ton of total time, it was not my first job or type rating either. I had flow for 3 previous companies and was fortunate enough to have several recommendations from other operators on the field including my most recent previous employer.
I don't think that there is anything harder in corporate aviation then hiring. Without a bunch of recommendations I think it's really a gamble. As my current chief pilot stated...almost anyone can fly a plane, but the key is finding someone that fits into the department.