I have tried to order episodes of "Hot Off The Grill" with Bobby Flay yet they told me that they do not have a distribution deal to produce DVD. In fact it appears as if their rights to even broadcast that series have expired. This is likely due to the fact that Hot Off The Grill included many celebrities, like Suzanne Sommors (Three's Company fame), and a co-host Jacquie Malouf. Many of these people may have not given rights to air any more than a certain number of episodes, so it makes more money to just forget about them and make new ones, like Bobby's "Boy Meets Grill" where he is the only person in most of them.
Yeah it's a messed up thing. Lots of great shows are just tossed with no real fans being able to see them, all due to licensing and greed, pretty much.
Call and write letters to Food Network and Scripps and see if you can get a response. Just my guess, but they don't really care what fans want to buy, only on what they can make the most money off of. Sorta like everything else in life...