I can only speak to the pilot stuff. Coming in off the street (Non ROTC or Academy Grad) without any previous flying experience and getting a Pilot Slot is nearly impossible (in the current climate) without serious inside connections (e.g. dad was a Squadron Commander). Most people trying to become an AF pilot off the street already have advanced pilot certificates and ratings...it is uber-competitive, 2-5% of applicants are selected to go to Pilot Training via OTS. Having your Master's may help you but its a long shot.

Now if you went out and got your Private Pilot Certificate...you may become very competitive.