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Scuff the clear on the headstock and shoot over it. Or sand it down to wood. When I did my headstocks I just scuffed up that was there put a white garbage bag over the neck and blue painters tape for the rest. Once you get you color coat down and it is just dry or tacky remove the painters tape at the edges and then hit with clear when done. I put my paint line up to the fretboard and then went up the ramped fretboard end with clear about to the nut to smooth it out.

Thanks for all your replies

If I don't make a complete dogs dinner of it and aren't too embarrassed, I'll post some pictures up!

Or maybe you'll just see a guitar on eBay with 'refinish done by a previous owner' - always makes me smile to see those kind of listings...