Yes, you will only send the guitar signal out, and will get each channel in each ear on your headphones, because that's how you panned them. The headphone jack replicates the panning that you set.
You'll just have to make sure that Path A and Path B are perfectly separated all the way across the chain in all your tones so that you don't apply any effects or amplification to Path B.
I actually never thought of this before, but you could assign Path B's Level parameter to a pedal controller, and adjust your own mix without having to have the sound guy do it for you!
Also, of course this set up means that you can never use dual amps/dual cabs, or stereo effects. You could always buy a small 4-channel mixer and connect everything so that you're still able to end up with the same In Ear mix while using both Pod outputs and the XLR coming from the PA board.
