Anybody on your 40 man roster can be added to your ML roster after the "Expand Big League Rosters" date. Any time spent on the ML roster counts as ML service time. I've always assumed that it works that way in real-life as well. If you have a reference that says otherwise, please feel free to post it. I'd be very surprised if that was the case.
Anybody who was on your 40 man roster as of the "Set Postseason Roster" date are eligible to be on your post season roster. Your post-season roster is 25 players, but you can adjust the roster before each playoff series (but not during) to add or remove eligible players. By default, the 25 players on your ML roster as of the "Set Postseason Roster" date make up your initial playoff roster. It's not uncommon to change your roster for the postseason because you typically don't need as many pitchers, so you can drop one or two and add an extra position player to act as a D-rep, PH, or PR.
Time spent on the ML roster during the postseason does NOT count as ML service time. Only regular season days on the ML roster count.