In reply to beardy mike:
It's always the tip of my big toe that hurts while I'm trying to break in new shoes.
I've been using Scarpa Vapour Vs for a while now. The last pair (which were the mk2 with a lot more rubber over the toes than the previous version) were hellish to break in, I suspect because the extra rubber prevented the toe box from stretching into shape for a while.
The current pair, the latest version, were remarkably comfy from the start. So maybe have a look at some of those?