Your phpinfo() was captured via browser (served by Apache) ... while PHP Interpreters in PhpStorm is a CLI thingy (i.e. to be executed in terminal). On some systems/setup (mainly Linux & Mac) they use different settings (different php.ini files).
You clearly have two different php.ini files used in both cases. For PHP Interpreters you have to edit that file that you have on your screenshot with PHP Interpreters (just click on Open in Editor link next to it).
- Your Apache uses
/Library/Application Support/appsolute/MAMP PRO/conf/php.ini
- PHP Interpreters one uses
/Applications/MAMP/bin/php/php5.6.10/conf/php.ini
You have to edit the last one and enable/configure xdebug there.
Keep in mind that PHP Interpreters will only be used if you execute/debug CLI scripts or other PHP-powered tools (like PHPUnit tests/CodeSniffer/PHPMD integration/Composer/Phing etc). If you only want to debug files served by Apache .. then PHP Interpreter is not required (and you can ignore what it says there).
P.S.
It's also possible that you may have more than one PHP installation on your computer (even if they are both the same version) -- double check that.
phpinfo()