For the posing I used Transpose Master to avoid any problems with the fibermesh SubTools. I mainly just transposed the leg and moved some of the other body parts like the head and arms to avoid symmetry.
I kept it really simple with the materials, since I knew I was going to do most of the work in post-production. Most SubTools got basic material 2, except for the fibermesh, which got basic material 1 with some extra specularity, and the body, for which I used skin shader 4.
Render and Post-Production
To render the image, I used a simple three-point light setup, and started taking out passes.
First I took a render pass with the main light and no shadows. That's the base I usually work on. If I think some parts are too dark in that render, I also take a pass with just the fill light. I just used the skin shader 4 and basic materials for this one, mostly.
Then I rendered the image with each light, this time with Shadows on and took only the shadow pass of each one.
Next, I turned off the PolyPaint in the whole sculpt, gave all the SubTools a Blinn material and, in the material settings, I took Ambient and Diffuse all the way down to 0 and gave it a low specular value. This way, I only got the specular passes with specular lighting and all the rest was pure black.
The next step was to make masks. I like to have masks of everything as it makes my life way easier in post-production. I gave each SubTool a flat material with a different color, contrasting as much as possible with the surrounding SubTools, and rendered that.
Finally, I gave all the SubTools a sketch MatCap or other shader that easily gave me a cavity pass, and took the chance to turn on Ambient Occlusion, ZDepth and SSS. I took all those images and moved on to Photoshop.
In both images I took out a lot more passes that only concerned some materials I'd made and wanted to keep in the final image. I would consider them exceptions. Those below are, I think, the ones that matter most.
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The main passes for this image