not everyone's legs go straight up. most people's bow outwards, some people's bow inwards, and others are more or less straight. you can see how much you need to set your cant with plain eyesight to some extent. in fact, good bootfitters will generally recognize this and mention something to the buyer. however, most of it is by feeling pressure yourself and recognizing that your boot needs to be adjusted.
in the op's case, it looks like an extreme circumstance that should be fairly easy to recognize the boot doesn't fit.
however, most of what i am saying is based on my limited knowledge and conjecture. there is an orange name "onenergykid" or something like that who knows a lot about boots (atomic boot tech i believe). you or the OP could pm if you have more specific questions. i'd assume he'd be able to help you out.