Out of shadows

I'm a bit late to the party. My first thought was also cel shading, though there are no enhanced lines. On second though, this could be a shot with a very fast film, giving a very high and dramatic kind of contrast. You're going for natural - the right lady looks a bit more naturally lit.

Yes, a negative specular can create the look of velvet on fabrics at certain times. Awesome to see you've discovered this on your own. Keep at it!

Thanks for info Rashad, i tried several diffrent light setups but i think this is going to take me a while, i am looking for that twighlight zone between full light and full dark, i did fix the cell shaded look by giving the main light source a negative specularity, it had an interesting and suprisingly nice effect on the clothing.

I see. Well the reason I ask about cell shading is because it mostly comes down to the blending. Currently all the blends are harsh, and not smoothed out. You will need to use softer shadows. True Ambience can only bounce light off of surfaces. Therefore, if you dont have and geometry in the environment you will get very little effect from TA. As you can see the TA is bouncing some light upward onto her face from the lapel of her garment. But that's about all you can expect. Now if the background is not really meant to be barren but merely to serve as a high contrast backdrop for a well lit foreground item, then our work is different. Id say then that you can add radials or IBl or domes to provide light from all sides in a way that flatters the target model.

Rashad, yes i forgot, i'm trying to go for realism, i know that the outfit does look a lot like cell shading, i'm more interested on the facial features and contrasts and blending of light and shadow.

Well, what exactly are you going for? It looks like a cell shading at this point. is there an environment? are you going for realism? Lots of questions.