First, include the libVLC library via Maven in Android. Then you'll create a libVLC instance object. You'll have to provide a file path of the media you want to play. You'll create a libVLC MediaPlayer and load the media into the MediaPlayer object. That MediaPlayer object will have commands like, start, stop, pause, etc... for control.
Whatever user interaction, such as buttons, you'll need to add onClick listeners that will signal your MediaPlayer object to start stop.
Here is a pretty simple example. You'll just need to link up your button events to the libVLC functions to control the MediaPlayer object.
https://github.com/wtud/LibVLCAndroidSample