Any water that would be in oil should be lying right in the bottom of the oil pan, with the oil sitting on top. If it is frozen on top of the valve cover, I have never seen that.
I would suspect failure of the head gadget, but again your coolant shouldn't freeze, and would produce a milky substance.
The fact that the oil filler cap was frozen on, is it possible that someone poured washer fluid into it?
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