1) The nav bar - it looks like you have several items there that all go to different places. Are you still having issues with that? Or is that just the sample and you want to customize it? Let me know and I'll help with that - this is an easy one.
2) Custom header? Like having a picture across the top where you currently have "Homegrown Memories Photography & Design" ? If so, the hard part is making the header, but you can probably do that in PSE no problem. It is off center because you haven't put in a center div section. I'll take a stab at this in a minute.
3) Color? I would start by picking the theme you want. That really is the basic way to get started and then customize off of the theme that is the closest to what you want. That way you don't have to do the work multiple times.
4) Another example? check out
http://www.2-dphoto.com and let me know if my customizations meet what you are thinking. At least somewhat. But pick your theme first. All other color choices and customizations flow from that.