Correct, CSW's boot punch will work on toecaps, but it requires quite a bit of heat and careful manipulation to get it to work.
Another thing to do is to try to get a little bit more room out of that skate by heating up the heel. The premise behind it is that you can get your foot to sit back further in the boot, therefore getting it off that spot on the toecap. Seems that the skate may be a tad small.
That is a bit of a weird spot to be feeling that though. Looking at it, I'm not so sure the CSW punch can hit that - might be in that area where it narrows.