Usually I unwrap the models specially complicated ones, and then I move to Photoshop to draw it. Applying unwrap modifier is a good solution (for me) for simple models.
If there are complicated models then I use UVW unwrapping software like Unfold 3D, it is very easy and fast.
In characters I used an opacity map that I paint in photoshop to give random effect in edges.
Tips
Apply unwrap modifier on deformable objects before deforming it to keep the right UVW coordinates for the deforming characters in this project.
Using “Composite” map is very useful in separating colors and blend layers by masks.
Shading
I used mental ray for rendering, really it is very good render and have helpful materials and shaders.
Arch-design material is excellent material and I used a lot and (pro-material) it is new material category in max 2009.
Lighting
I used 3 area lights, one is spherical on lamp and others are rectangle and you can see more in the following image and note that the intensity of light is depend on the values of exposure controller, I used mr photographic controller and it is really very good and suitable for mental ray scenes.