If your speakers have transformers on them, you're halfway there. I would use a 25 volt reference audio level, which is probably easily available from your amplifier (75W/ch). At each speaker, you select the transformer tap (in watts) that represents how much power you want in that room at maximum volume. For a simple system you don't have to boost the amplifier output to 100V.
Note: If your transformers are labeled 70.7 volts (a common type) then the 10W tap is actually about 1.25W, 1W tap is 125 mW, and so on.
The total power selected by all speakers must not exceed the amplifier rating. (You can calculate impedances but this way is simpler for a novice.)