$re = '/\bPlus\b(?![^>]*<\/h\d+>)/m';
$str = '<h4 class="Somethingsomething" id="something">Plus plan</h4>The <b>Plus</b> plan starts at $14 per person per month and comes with everything from Basic.';
$subst = "{{Provider_Link '$&', 33}}";
$result = preg_replace($re, $subst, $str);
echo "The result of the substitution is ".$result;
Please keep in mind that these code samples are automatically generated and are not guaranteed to work. If you find any syntax errors, feel free to submit a bug report. For a full regex reference for PHP, please visit: http://php.net/manual/en/ref.pcre.php