I'm able to use the color picker tab (available from the 'Materials' command) to change the color of a solid- is it possible to change the color of a single face on that solid? Selecting the face and using the picker results in no visible change.
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With the geometry to modify highlighted/selected and the Material Browser open. Try right clicking on the desired material in the Material Browser (visual tab) and choose 'Assign to Selection'.
Check out this video for further detail.
http://screencast.com/t/K5KLRquH
Hope that helps.
Thanks,