so there are several ways you can add a stylesheet in OpenCart themes
the simple way
in file catalog/view/theme/YOUR_THEME/template/common/header.twig add the link to your stylesheet in
< head >` right after your last css file.
remember that your custom stylesheet has to go after your default stylesheet for the styles to override them.
<link href="catalog/view/theme/YOUR_THEME/stylesheet/CUSTOM_STYLESHEET.css" rel="stylesheet">
the more sophisticated way
OpenCart allows you to set the stylesheet from the contorller. this is often used by modules to add their styles to the head tag and also allow site optimization modules to compress the stylesheet file.
you can test it by editing a controller file for homepage (as an example)
in file catalog/controller/common/home.php
on line 7
add this code
$this->document->addStyle('catalog/view/theme/YOUR_THEME/stylesheet/CUSTOM_STYLESHEET.css');
I hope this helps