I would imagine it's more likely to move from an MA in a related field to a PhD. What would your PhD be in? I know several people with underwhelming undergraduate histories who have gone that route with mixed success.
The biggest detriment to pursuing an MA outside of a PhD is the cost. But, because it sounds like you're going to utilize military money, that shouldn't be a problem. With regard to your question about admissions, having independent funding is definitely not going to hurt you.
My focus would be to make sure that there is somewhat of a linear trajectory from MA to PhD (ie: MA in international relations to political science PhD). When I think "professional-oriented" masters in this field, I tend to think MPA/MPP, which are not necessarily a great transfer to a political science PhD.