Part of the problem might be because you're working with rigged figures. In Poser, to use the grouping tool, you need to work with each body part separately. You can't create a group while the body is selected and if you have the hip selected, you can't add polygons from the arm To create material groups open the grouping tool. Add a new group.

Select polygons you want to change the material for.

Click on assign material. type a name in the box and click okay

Switch to the next body part you want to work with. Add a new group.

Add the polygons you want to change

Click on assign material and scroll to the material you already added, or add another new one

repeat with each body part until you have them all changed

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