What you do is make the material in the Pose room, using the grouping tool. Create a new group. The name doesn't matter, I just use the default name. Use the Add All button. You now have a group comprising the whole object. Make a material (and the name does matter for this), and then delete the group. If you want to make an item with several materials, you need to keep the temporary groups. If you wanted to have some buttons, for instance, assign the burrons to a group. Then make a new group, Add All, and remove the button group. Each group can now be made into a different material. It can be useful to make material groups which match the seams of clothing. Think of some sports shirts where the sleeves might be a different colour of fabric. Or the material could be set transparent.