Thanks for the extra information joliett89, this concerns me:
It was made to look that way to get people to pay more for redesign after buying the script.
Given you want to modify/re-design the script, and the terms of purchase specifically require further payment to do so, it sounds as if your plan would be a direct breach of the terms of sale/purchase.
However, in terms of your goal, in very simple terms, Smarty is a templating system based on php, ajax is based on javascript and together they produce the html and css that is output to the browser. To understand how this "fits' together, I suggest you start by analysing which parts of the html document are being output by which scripts. That would probably require some knowledge of Smarty and Ajax (and their underlying technologies). Once you understand how the html is produced and have modified the back-end scripts to delete/modify the functions you do/don't want so you have the html you require, then focus on using css to style it.
I realise this is the reverse of your original approach, and doesn't answer the question you originally asked, but css styles html, so is last in the "chain" of delivering content to a user.
Another approach, and what will be necessary if the terms of sale/purchase prohibit modifying the templates as I suspect they will, is to re-write yourself. That would require analysing your pages to identify what components you want. To use a very simple example, each page might be static, with a carousel for showcasing movies. That could be easily coded in html, with a freebie php/javascript script for the carousel. However, while that might work for a smaller site, it could be unmanageable for a larger site with lots of movies that require some form of databasing.
While we can help with the css, given your overall goal (assuming you are not prohibited from modifying the templates), I think it would be worthwhile asking about the best way to manage the site in the CMS (Content Management Systems) forum, or perhaps PHP - which seems to get lots of questions about Smarty itself.