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For perspective, I finished my BS and AS degrees while enlisted in the Navy, took me 9 years from zero credits to completion. I didn't work that hard on it, honestly, if I pushed harder, I probably could have done it in 5-6 years comfortably ( as in, 2 classes a semester [each semester only 9 weeks long for my school, each class only meets once a week, with homework to do) However, during that time, I also worked very hard in my professional job and advanced from E-1 to E-6 in 7 years.
It's all about what your goals and motivation are at the end of the day. You want a balance of school and work success, or are you trying to go all-out school and get done within your first contract? (usually 4-5 years)
I'd suggest Guard/Reserve, if education is what you are seeking then strive for that. I know in the Air Force you can work on your CCAF, but if schooling is all you are interested in; go for it. If you still want to be in the military later, commission in.
I personally can only speak for the Air Force side of things, however I'm sure all branches encourage you to go to school. The Air Force is very big on school. You are expected to have certain degrees in order to get certain rank. (It is one of those "unwritten rules" of the game.) What is more important than service though is the job. If you are working a job where you are working rotating hours and don't have a set schedule (any 24 hour operations type of job) it is very hard to take in-class classes. However, online is always an option. The most important thing if you are thinking about college is what job you would be performing in your enlistment. Another option is to do any branch's version of the National Guard. Some states will pay for your tuition 100% while you serve and you are only required to go into the office 1 weekend a month, which you get paid for. It's a great gig if you are really just wanting to get your degree. You can check out the different States' benefits for Air National Guard (The Air Force Guard) at: http://goang.com/Benefits/Benefits. If you click on the "State Benefits" tab you can select what States you might be interested in serving in and see what benefits they offer. Only some states offer the 100% tuition assistance. The guard is also cool because you can volunteer to deploy whenever you want (for the most part) whereas on active duty you are tasked and you have to go. I'm active duty Air Force. I love every second of it and am taking classes towards my degree now. However, if your priority is school and not so much an Air Force career? I would definitely go for Air National Guard and take advantage of their Tuition help.
Side note: **EVERY BRANCH HAS THE SAME EDUCATIONAL BENEFITS AS FAR AS FUNDING IS CONCERNED** The only MAJOR difference is that in the Air Force ALL of your job training is college credit. This is the ONLY BRANCH that does this. The Community College of the Air Force is an accredited college. For instance, Basic Military Training is a 3 credit Physical Education course. Through your career training you can earn an Associates of Applied Sciences Degree in that field. NO other branch can offer this.