How can I use PurifyCSS to clean WordPress style.css?

Optimizing the CSS for WordPress is a time consuming job. You will have to consider all pages (404, archive, search, etc) as well as every possible element that you can think of, such as images, ordered lists, un-ordered lists, quotes, galleries, etc.

Not to mention that your theme might use some sort of AJAX or modal that could be loaded only on special events, such as errors or notification.

Still there might be some classes hidden from purifyCSS.

In my experience, I think it’s better to first cover the WordPress generated classes and then browse the theme for classes, finding them and storing them in a separate CSS file, until you finish reviewing the theme.

Also you might want to look into functions.php file for possible shortcode and AJAX handlers, outputting HTML content.

As i mentioned, it’s a really easy but time consuming task to accomplish, since the automated apps can’t extract it all (at least on the front-side).