CLI is the command line interface. You can find it in accessories or pin it to your start bar. Right click and run as administrator. You'll need to track down the location for where you installed it, probably in program files if you didn't modify it, and the *\bin directory of the apache install will include the httpd.conf.
I would uninstall that one myself. That's a relatively old version of Apache, and you'll need a newer one to support 5.4 PHP versions.
Go here: http://www.apachelounge.com/download/
Download one of the newer versions (2.2.23 or 2.4.3 preferably). Also download the VC9 compiled handler for your php version under the modules. That one is under php5apache2_4.dll-php-5.4-win32.zip for example for 5.4.
Then go here: http://windows.php.net/download/#php-5.4
and download a version of 5.4 PHP. Use a .zip install for win32 VC9 thread safe. Extract that wherever, drop the php5apache2_4.dll into that directory, and extract the apache download wherever. Configure the httpd.conf and php.ini, then use the command line to install the httpd.exe -k install options.
Or you can use wamp as well. I hear its easy to install, and its just a bundled version of apache, mysql and PHP. That would save you having to get a mysql install as well. Personally I find all three of these easy to install, but I've also been doing it for over a decade.