Do not do this, as it will crash the game (unless they fixed that in the interim). Rather, use
player.setav ###
where ### is an integer value from 1-100
This will set your skill to the new value, while still allowing it to be raised later if you see fit. It shouldn't be an issue, though, since they presumably carried over the code patch from FO3 that allowed one to skip the skill point allotment screen if all skills were maxed out. At least I hope they carried it over, since it's possible to cap all 13 skills by L42, or about L35 if one uses certain attribute-boosting glitches.
Normally I'd say I will find out soon enough, but I don't want to spend that much time.
Unless of course I set everything to 100 right before I reach the next level, and see if it works. But that will happen in a few more thousand EXP. If it works, then I'll keep the save, if it doesn't I just reload the save to save time.