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Vector objects have just one fill and stroke property each.
However, you can duplicate your object, set the fill to "none" and give the duplicate object a different stroke.
Thanks pixlor! Not the easiest way, but better than nothing.
Use an inner glow for the first outline, and the Photoshop Live Effect Stroke for the second.
Thanks, but this doesn't work for me. The two strokes do always have the same color. No matter which one of them are the inside or the outside stroke.