Here is an interesting read on non-exuvium sexing.
www.birdspiders.com/faq_sex.php
I think the point is that it is possible to sex ventrally, but there are hard and fast rules. It has more to do with the type of setae and not the furrow that we usually look for.
One interesting bit is where the author states that at VERY young age, the exuvium of the male has a more apparent furrow or pocket(not used for sperm) than the females spermethecae punch that will develop later.
Even upto the day that I sold my fairly large P ornata male, I thought ventrally it looked like a female, but the exuvium doesn't lie.
In the end, I think if any breeders are "sexing" slings (only possible from 2nd instar exuvium onwards), they are still taking a gamble.
Most breeders start selling slings at 2nd instar when they are eating. Some species only start eating at 3rd instar, at which point they are only sellable. So not always possible to sex them before they are marketable.
but selling 5 and 6th instar slings without them having been sexed is also possible. My one avicularia and P cambridgei has destroyed their molts all the time. I was only able to sex them both (as females) by waiting for them to finish and immediately removing the shed, while it is still soft.