First idea is that display_errors is also turned off
error_reporting(E_ALL);
ini_set('display_errors', 1);
Second idea is that you have error in your main script and it is not able to switch those options (for example parse error) - in this case you can try to include that script into another one like below:
<?php
error_reporting(E_ALL);
ini_set('display_errors', 1);
include('index.php');