Are you talking sole canting or cuff alignment?
Sole canting involves the installation of wedges under the boot to correct for a bowlegged or knock-kneed stance. What's involved here is going to a boot fitter, having your alignment checked and then they grind down the sole and the tops of the toe and heel lugs at an angle and install wedges underneath. When bowlegged, they prop up the outside of the foot to force the knees in, and vice versa for knock-kneed.
I'm assuming you're talking cuff alignment, which is what most boots call canting, done by loosening the pivot bolt on the side and changing the angle of the cuff. The proper way to adjust the cuff is by standing on your footbed in the bare shell (no liner) and adjusting the cuff so that there is equal space between the inside and outside of your ankle and the shell. When checking, make sure to flex forward to see the trajectory of your shins and take that into consideration when making your adjustment. Ideally, you shouldn't need to move the cuff much from centre, and if you do, you should look into getting a custom footbed to support your arches, and then do some sole canting.