I think that gramatically it should be photo shoot but both that and photoshoot are widely used and as language is a living thing I guess either is acceptable. The on-line Oxford Dictionary only lists it as two words but that isn't really definitive. I've also seen it hyphenated - photo-shoot - but that doesn't appear to be so widely used.
Whichever way you choose to use it, an upper case "P" is only appropriate at the beginning of a sentence and I can't (off-hand) think of an instance where shoot would gain a capital "S".
Google counts both as the same thing. I just did a check on Doncaster and it brought up a very similar set of results with and without the gap (and I'm all over it and never use the gap).
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