For more volume, you should be thinking more speaker cone area (more speakers or bigger speakers or both).
The reason for running two amps are to let each amp shape a different part of your tone.
Some folks
biamp. This is using a stereo or 2-channel amplifier with a crossover, so one side handles the bass frequencies and one side handles the trebles.
Some folks use 2 amps and just tune them by ear to what sounds good. It's not true biamping because there's not a crossover.
The potential drawback to using 2 separate amp/speaker systems without a crossover is that if they're both sending out the same frequency on the EQ they could be cancelling each other out, or reinforcing at that frequency, or ?. Also, if the speakers aren't matched they can be slightly (or a lot) out of phase with each other, which (to a layman like me) sounds like "there's something wrong but I can't put my finger on it".
I have had good success using an Eden WT550 head + Eden D410XLT cabinet for lows and low mids, and an SWR Redhead on top for the highs. I EQ them so the Eden doesn't try to go above 800 Hz and the SWR doesn't try to go below about 600Hz. This is tuned by ear. I didn't use a scope to see where the true freq response of each system was.
One advantage of dual-amping if you use a lot of effects is that you can send the effects just through the treble rig so they won't muddy up the bass, if you like that kind of blended effects tone. Doesn't work so well with pitch shifters, though
A lot of folks will tell you mismatching gear like that is a crapshoot and it's true. I got kinda lucky. You should listen to the equipment you're thinking about before laying out cash.