You can apply HTML markup to the usernames of people in different usergroups. If you are going to do something simple like a color or a font-weight, then inline CSS would be fine to use.
But, if you're going to add a lot of CSS, and perhaps :hover and/or :active classes, then I recommend defining CSS class selectors that are either in your "additional.css" template(s) or added via a plugin (which is the method I prefer because then I don't have to worry about adding the CSS to each new style).
Then, do some online searches to determine the CSS you need for the effects you desire.
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