I've been experiencing the same issue. I even just tried restarting the computer and nothing changed. But then the other day I tried again and it popped up!
I use Windows 8, not sure if that my the problem or not, but when I plug the S4 into my PC, I do hear the the little USB device connection sound that W8 makes, just can't actually see my device!
EDIT: Also I just noticed, it probably would have been better to post this in another sub forum rather than this one...