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This is already posted on the Regular Expression subforum but perhaps it really belongs to general.

Is it possible to use regular expressions in Syntax files? Or at least be able to highlight a word that begins with a particular character. For example, $, @, or % in Perl: $abc, @def, %ghi.

Regular expressions in syntax files are definitely not possible. I'm not 100% sure about highlighting words that start with a certain character, but I don't think that can be done either. See the help topic "Syntax Definition Files" (Help | Contents | How To | Customize settings | Syntax Highlighting | Notes).