Let's see if I can help. I assume that you are working with an editable poly. If not, convert it to an editable poly and select all of the faces. You will have to reset the face to a single material ID. When converting a box like this, if you check the faces on each side of the box, you'll notice that it gives a different material id for each side.
Step 1: Change all faces to "1" under the material id by selecting the entire object.
Step 2: Now, select the faces that you want to represent material id "2" for your second color.
Step 3: Open up the material editor. In the first and second slot, create your first and second material. In the 3rd slot, select the button circled in yellow to bring up your material browser. Select "Multi/Sub-Object and close the browser.
Step 4: The default is set to 10 different materials. Press the "Set Number" button and change this to "2".
Step 5: Drag your first material, white in this case, down to the slot label ID 1. Then drag your second material down to id 2. Once this is done, your 3rd slot should look like a checkered material with your two colors. From here, just assign your material and you should have "white" on "Material ID 1" and "red" on Material ID 2.
I hope this helps to give you a better understanding of how Multi/Sub-Object materials work.
Moderator
Step 1: Change all faces to "1" under the material id by selecting the entire object.
Step 2: Now, select the faces that you want to represent material id "2" for your second color.
Step 3: Open up the material editor. In the first and second slot, create your first and second material. In the 3rd slot, select the button circled in yellow to bring up your material browser. Select "Multi/Sub-Object and close the browser.
Step 4: The default is set to 10 different materials. Press the "Set Number" button and change this to "2".
Step 5: Drag your first material, white in this case, down to the slot label ID 1. Then drag your second material down to id 2. Once this is done, your 3rd slot should look like a checkered material with your two colors. From here, just assign your material and you should have "white" on "Material ID 1" and "red" on Material ID 2.
I hope this helps to give you a better understanding of how Multi/Sub-Object materials work.
Rick
[Link to www.3dartconcepts.com]