Rewrite URL to get rid of wp-content etc and change URL

$matches[1] doesn’t work for external redirects, only internal (URL must start with index.php and handled by WordPress itself)

Try this

add_action('init', 'custom_rewrite_pdfURL');
function custom_rewrite_pdfURL() {
    add_rewrite_rule('^carPDF/([^/]*)/?', 'wp-content/themes/exampletheme/templates/pdf-generator.php?productID=$1', 'top');
}

Don’t forget to flush permalinks

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