1) Which is better to use
http://www.site.com or site.com?
It doesn't really matters which one you use. But search engines treat http://www.site.com different to site.com, i.e. two different domains. So it's best to use one, whichever you decide to, but make sure the same is used all over.
2) Which is better / or /index.php
Again, it's not much of a matter, but use one of them since they may be (by few search engines), considered as duplicates.
3) Is it better to put content in it's own directory or site.com/article.php?
Directories provide additional keywords for the url. For example:
domain.com/articles/make-php-run-fast.html
Is better than:
domain.com/make-php-run-fast.html
Although that only has a slight effect.
4) Is there anyway to SEO images?
If you're talking about your images getting indexed in Google Image search, then you can use descriptive file names such as Rotana_Beach_View_Beautiful.jpg instead of rotana001.jpg .. Or if you're talking about optimizing your image gallery pages, then surely you can use descriptive titles, descriptive file names, and a reasonable description (text snippet in the html) for the image. Such as "The rotana beach was looking amazing in the sunset."
Hope that helps