The comma, like in all identifiers, is splitting up the string into 2 different parameters. Try this:
$regex(<option value="SIT">Slovenia $+ $chr(44) Tolar (SIT)</option>,<option value="([a-zA-Z]+)"\w*?>(.+?)</option>)
I changed \w+ to .+? since Slovenia, Tolar (SIT) doesn't just consist of word characters but also a comma, parentheses and spaces. Also, [\w]* can be \w* but I added the ? to make it non-greedy, so it doesn't capture as much text as possible