I know a handful of couples like that. It was pretty painless --so long as they married prior to coming to the US. So they were legally married overseas, then applied at overseas consulate and green card was granted --citizenship can be applied for a year after arrival, and (I'm under the impression) most have been granted citizenship within one to two years. No fuss, that I've heard of.

Now, (you) working overseas (not in the US) as a non citizen can get tricky for US citizens --you have to be sponsored, of course, but in some countries, like Argentina, you (or employer most likely) would have to prove there was no local available to fulfill the job requirement. That can be a tough hurdle.