I don't think the full time 4wd aspect has any bearing on alignment requirements (unless maybe the rear wheels actually have a steering mechanism for cornering).
An alignment adjusts the caster, camber, the toe position of the wheels.
An alignment should be done whenever you change something that might affect the geometry of the steering of the vehicle. So if you lift/lower the suspension, change out the steering components, or change to a different size of wheel/tire combination, relocate the front axle, etc. OR if you happen to "knock" the vehicle out of alignment due to some kind of sudden impact. Sypmtoms can be the vehicle not tracking straight when you let go of the steering wheel on a level road surface and feel the steering pull to one side or the other.
If your vehicle tracks straight, and you haven't made any mechanical changes, and your tires are wearing evenly, I don't see any reason to really get one.
My most recent alignment cost $52.
[EDIT] LOL, Henry beat me to it.
[EDIT #2] Sorry, forgot to answer a question. There are generally shops that specifically do alignments, and often that are also doing brake service. (e.g "XYZ Alignment & Brake service") I think the best bet is to check with friends to see if they have any luck with a particular shop in your locale. Like any profession, there seems to be good ones and bad ones.