If it's just little samples you're looking for, then most companies will happily send you out small sachets etc to sample since they cost next to nothing, but you have to contact them and explain what you're asking for, ie. 'i'm looking for a new pedicure range and would like to try a couple of sample sachets'
If it's bigger items you are looking for the best way to gain these is simply to be methodical with your buying. Buy your items in bulk all at once, say once a month or so. That way you have a large order which a company will very often throw in a few freebies into. You also have more power to ask for something for free with a larger order as you can point out the amount you have just spent. Even if you have spent the same amount over several orders, it doesn't make the same impact as buying all at once.
The only way you can find out is to ask, the worst that can happen is they say no. But you can ask why? IIf they give you an explanation then faie enough, but if they can't then just just point out that that is unhelpful and so you won't be able to take on their product if you can't try it.
As for enhancement product samples, these are not usually free but are usually sold at just a few pounds, which is not a silly amount to spend if you're serious about researching a product.