I would have mixed feelings about being a Peace Corps physician (this is based solely on my experience as a volunteer). Peace Corps has an NP or RN in every country with volunteers, but only one physician per region. The doc is usually based out of the largest city in the region, and gets to travel extensively throughout the region. But most volunteers have limited contact with the Peace Corps doc, and the physician is more of an advocate for the PC administrations interests than s/he is an advocate for the patient, imo.
I want an international medical career, too, and I'm not quite sure how I would incorporate it with practice here. Doctors without Borders appears to get commited, experienced physicians, but they also cover wide geographic territories which limits continuity of patient care. Realistically, it might not be a commitment I could make until retiring from practice here. I'm not sure.
There are also doctors heading up nonprofits in Africa (the aid parade) but these people are rarely practicing full-time, from what I could gather.
That's the little I know. I totally understand the desire to work overseas. You want to check out opportunities carefully, though, particularly if you've never worked overseas before (and even more so if you have).