Steve,
As others have suggested I would contact your companies flight department to see what the chances are of getting hired there. This is a "who you know" business, if you dont know anybody, you dont have much of a chance.
At Flight Safety last time,I met a guy who was hired to fly a Citation with 500 hours. He had worked the ramp for this company and they sent him to school as soon as he met insurance mins for the right seat. Now he's in a Challenger 300 with less than 1500 hours. This sort of thing happens but is very rare.
In my opinion the most important thing you have to consider is how this is going to effect your family. (Sorry, dont remember if you have kids or not) This businees can be brutal on your family life. You will miss many weekends, holidays and other important dates. You will almost certinaly have to move at least once. And your family income will be cut nearly in half for several years.
Is your wife a very independant person? Is she going to be willing to pick up alot of your slack because you're out of town? If not, this probably wont end well for your marriage. (Sorry, just being honest) I have known my wife since I was a student (she knew what she was getting into) She is very independant and it is still hard sometimes.
Looking at the financial end of this, consider: It's going to take you at least 5-7 years (maybe more, maybe never) to get to your present income level. That will make you close to 50 by the time this happens. Figure another 5+ years to make up the lost income of the first 5-7 years, your now in you're early to mid 50's. Your ratings are going to cost you 10's of thousands of dollars, tack on a few more years to pay for that. Now you're in your mid to late 50's (at best) before you break even financially. You will have maybe 10 years of higer income as a pilot. Thats assuming you dont lose your medical before you want to retire.
The corporate side of this business is far superior to the airline side (I've done both) but it is harder to break into. Also, the difference between a good job and a bad job is much larger in corporate. Also, there is very little job security. If the company decides to sell the planes, they dont have much use for the pilots. This never goes away no matter how much seniority you have. If it does happen, you will likely have to move again.
To get your foot in the door with your companies flight department I would suggest the following: Call up the Chief Pilot and offer to buy him lunch in exchange for his advise. Tell him your whole story and what your goals are. Ask him how he got to where he is. Be willing to help out around the hangar (for little or no compensation) this will show him you are serious and if you do a good job, will make him want to help you. Hanger floors always need to be cleaned.
This may sound a bit off-putting, but remember you are trying to take a HUGE career short cut here and your are going to need this guys help. The other thing to consider is, if he cant help you, he may know someone in the area who can.
If you can get your foot in the door with the flight department at your current company I would go that route. If that turns out to be a dead end, I would recomend you dont do this. The potential reward is not worth the risk to your income and family life.
Sorry to be a downer but, I have given your situation a lot of thought and this is what I really think. I have a very good job, but It took me +10 years of CFI'ing, delivering planes, Freight Dogging, crappy airlines, commuting, flying charter, etc to get here (and some luck and help form many friends) Still, for every pilot I know with a good job I know 2 that are unemployed or underemployed.
You have a decent job with a well above average income and a good family life. Dont risk that. 5 years from now I hope you are the manager of your current department, not living in a 1 bedroom appartment in West Virginia, flying cargo, making allamony/child support payments. (i'm thinking of a friend of mine)
Best of luck, no matter what you decide to do.