It's really easy. I haven't done online booking yet, but presume based on reports so far that it'd be easy to do online, too...
But for calling in the reservation, just call MS ... tell them you want a 1-BR on the date you want and the resort you want, and tell them you're making the reservation for someone else (you can say it's a gift to your sister, but you don't have to and they probably won't ask).
They will need your sister's name, address & phone number, and the names (and ages of children) of all who will be staying in the villa.
Voila--done.
They'll read you a confirmation number, and then email you a confirmation (altho it'll show up basically instantaneously under "my reservations" on the dvcmember website...I usually have that site open when I call, and virtually always the reservation shows up there before I conclude my call w/MS)...
They'll probably ask you if you want ME and/or the dining plan (easy to say "no" or "not yet"...if you say "yes" you'll have to give them flight arrival info for ME and payment for the dining plan)...they will probably also ask you for a credit card number...just say no. You are not required to put down a credit card, ever (and certainly not for someone else), but they've gotten kind of pushy about asking for one at booking these days.
Good luck!