The theory with Barbour type wax is that you block the holes in the weave with wax so water cannot get through. The disadvantage here is that it cannot escape either, so the clothing cannot breath and you can get moisture inside with sweating.
The Nikwax approach is to coat the cotton fibres which will make the hole in the weave smaller, too small for water droplets to pass through. However, it's not too small for water vapour to pass through. This allows your sweat vapour to escape, so the clothing retains it's breathability. I believe that is the advantage of Ventile and Goretex (though if i'm wrong, a certain Mr Fenna will probably be along shortly to put me right!).
I personally love Nikwax, so much so that most of my clothing get's a treatment. I have devised a Nikwax tactic which i mentioned quite a while ago. I came to this conclusion when i first started using cottonproof (then called TX-10) in the early 90's.
1) Wash the item in a washing machine ensuring you do not use any detergent and that the machine draw if free from soap.
2) Using Cotton proof, wash the garment as per the instructions on the bottle while the garment is still wet.
3) Repeat step 2 a second time.
4) Repeat step 2 a third time
This is your initial proofing. When it comes time to wash, use Nikwax wash and then reproof (once only this time). Hey presto, job done. It has to be said though that this may only make the garment heavy showerproof and that, for total waterproof, your best off with a dedicated waterproof garment. Having said that, i can't fault it!