No, it will just make what you see agree with what everyone else sees. his head is already picked.
You picked... lets say hypothetically, head #16. You had an override that made head 16 look like you saw it on creation. However, the layo pack has head 16 as a different head.
So, doing this will prevent you from having this problem when creating characters in the future, but it will not change your already created characters head from the one it is now (the slick hair and piercings one) to one that you like. it will stay at head 16, everyone else will see what they always saw, you will just see what everyone else sees too.
The only way to change his head to the one you wanted is to have L or Orth LETO it (edit the character file in the server vault.) Which probably won't happen, since it takes time, and if it were available as an option people would be requesting their characters LETOed all the time.
-TV