I just read your post. I've always been a fan of giving someone the benefit of the doubt. Plus, i've always wanted to trust people when they're telling me something. However, my husband lied to me many, many times - I came to find out later. Then, whenever he told me something, there was always an element of doubt in my mind if it was the actual truth.
In your case, I would ask him again. Reason I say this is because I thought his answer was in a way, evading your question. I'm sure it was makeup. Just tell him that you know makeup when you see makeup and that you'd appreciate that he be honest now. Once there is a trust breakdown, it's very hard to build it back up. I know it's tough to have to put your husband "on the stand", but you've got to explain to him why it's upsetting you - tell him to try and see it from your perspective.
On a side note, i'm not sure how often your husband stays out until 5:00 am - maybe it was a one time thing. But, don't let that lifestyle continue. You can't change him, but you can change how you deal with it. You don't have put up with a guy who doesn't have any concern for your feelings.
I wish you all the best in your situation.