Well, the same skill set you look for for any game programmer, but with XNA knowledge as well. Depending on just what exactly you're looking for of course you're going to want to know what games they've worked on before and take a look at their resume and portfolio. The XNA framework is very new so you're not going to find many published games with it (in fact, there's currently only one I know of with a few more in the wings), but if you need an experienced game programmer, they should have experience with other framework and languages with games they have developed and released.
Along with that you're going to want to check the requirements for the job. Do they need networking knowledge? Do they need to know how to build and scale a game to support large amounts of players? Do they need to create something original? Would experience with a Physics API you have in house help?
Honestly, there's not much you need to know about using the XNA framework (other then some exposure to it and familiarity with C# development). The real key is just game development experience in general. Of course, if you're looking for a total newbie, just ask them to show you their current projects. If you like what you see, then sounds like you have your candidate.