There was great discussion some long time ago about the fast and slow feathering gene, I believe it was made by ipf and many others contributed to it. For sure, some breeds, the light Sussex and light brahma are two that I can think of, that can be feather sexed. I also find that the blue and splash cochins can be feather sexed, most of the time, but the blacks, a mystery until about 6 weeks of age, most times, other times, can be early sexed too. I have now and then when sexing blue and splash cochins thought the gender was correct, until about 6 weeks of age, when that sexing was inaccurate. I do not sex cochins now until they are about 5-6 weeks old. Mistakes can be made. Critical mistakes.
Buff orpingtons are slow and fast feathering. I have found that MOST females feather out very fast, like within a week, huge differences. BUT on the other hand I have had a slow feathering female come about, which I thought was a cockerel. I do not feather sex buff orpingtons now until about 5-6 weeks old. Had I used that method of the slow and fast feathering and not kept cockerels, I would have lost many a pullet. They cannot be accurately feather sexed until older, as I said. My experience, others may feel differently. I'm with you Jonny on what your observation is. For sure with the buff orpingotns anyways, the females do indeed have a much more round looking heads, boys are more pinheads, smiling (a little tease on boys here).
I truly believe that light Sussex, as Coopslave too said, can be feather sexed, probably at even a few days old. I do not trust feather sexing with cochins nor buff orpingtons until they are past their third week in life. Then pretty much clear who is who in that zoo. Have an awesome day, CynthiaM.