In many settings there are characters noted to be very distant from the concepts of humanity ("you shouldn't kill", etc.). In Vampire: The Masquerade there are plenty of such creatures, and in most cases when someone tries to roleplay such a thing, it looks... funny. A humane player will almost always fail to understand how is it like to be inhumane. To understand vampires of very low Humanity one may try to learn about serial killers from our world -- but even this barely helps. And I have totally no idea about what to do with those who abandoned their Humanity long ago, and follow a Path of Enlightment, especially those that use Conviction and Instincts. Players just can't understand how does it feel when Humanity doesn't bother you at all, and even if they strictly follow guidelines of their Path, they still strive to keep following Humanity even if they don't understand that they do.
For now the only way to solve this problem that I found was to simply disallow players to start on Paths of Enlightment or on low Humanity, except for those few players that I know of as distant from Humanity in real life, so they have no problem in roleplaying inhumane characters. But it's not good to just cut off a huge portion of the game, and characters may lose their Humanity while playing.
This problem wouldn't be that strong in tabletop, where the GM has a direct control over everything going on, but I mainly deal with LARP, where GM shouldn't interfere in most interactions, and hence has almost no way to deal with it when it is happening right now.
Long story short, how to deal with roleplaying characters who follow moral codes that are very different from players' moral code? I would like roleplaying methods over mechanical methods as a solution.