I think Huggyu2 gave you pretty much as real an answer as you're going to find. It is VERY competitive to get a pilot slot in the Guard/Reserves. You would be in a decent position if you were to actually have multiple pilot slot offers. Meaning, in my humble opinion, chances are ANY of these pilot slots are worth more than your current 121 employment. As a matter of fact, even as a part-timer, you are probably able to pull more money in the Guard/Reserves as a bum/trougher than most 121 employer's junior year payscales, not even a question if we are talking regionals. So, I think that's where you got the sarcastic responses; your current 121 employment would probably be the "complementing" job to the Guard/Reserve job, not the other way around; at least until you get to your "dream" major job, and then it would still see you through the first year payscale. Also, I'm not saying you intended to, but I think it may have been misunderstood from your post that you may think having 121 time under your belt make attaining a Guard/Reserve slot a done deal. It doesn't really.
Now, to answer your question, there is no visible difference in a pilot job in the ANG vs. the AF Reserves. The ANG has a state mission in addition to the federal mission, but from the perspective of a pilot, this is a non-issue. The pay system is the same, the job nature is exactly the same, the drill system is the same. The workload, availability of orders, activation rate is all dependent on tons of things, none of which is whether they are Reserve vs. Guard...for the most part. They are in essence the same.
The application process is a little different in the Reserves, but not much. In the Guard, you apply directly to the unit you wish to work for. IF you get an interview, you go through that and if lucky, or your daddy is the WG/CC (sorry, had to throw that in), you're in. In the Reserves the process is the same as far as applying to individual units and interviewing, but at the end of that step, your application package gets submitted to a National pilot board that is held twice a year, where packages are either approved or dissaproved. For guys who get hired with the unit, their packages are "sponsored" by said unit and sent to the board. 99.9% of sponsored packages are approved. It is in essence a rubber stamp. The other option the Reserves has available is the unsponsored package, in which you send your package directly to the board as an individual civilian under the sponsoring of a regional Reserve officer accessions recruiter. Under this method, you go through all the paperwork hoops as a civilian with the "help" of the recruiter and he/she submits the package to Robins AFB (AFRC HQ). If your package is approved as an unsponsored applicant, you then have to go look for an employer..i.e. a unit. Some people consider the process to be a waste of time because you would still have to pimp up the individual units and get an interview with them, just like the dudes who interviewed and went to the board sponsored. I can tell you it's a lot different going to a unit with all your paperwork approved, it's just like being a free agent. Plus if you were to get hired, you would get put on orders on the spot, as you were already approved. It is the 1% route, but I can vouch for it, as I gained access to the Reserves as an unsponsored guy.
That's the skinny on Guard/Reserves. Good luck on your quest. Oh yeah, and for the most part, Guard Reserve jobs are pretty much ideally set up to work with the airline work schedule, much more so than the 9-5er.