You can change the active behaviour to the VLC behaviour via 
AppleScript like this:

tell application "Remote Buddy" 
behaviourcore accessor "setActiveBehaviour" identifier 
"org.videolan.vlc" useActivationEventCode "activated" 
end tell

or to make the selection "sticky"

tell application "Remote Buddy" 
behaviourcore accessor "setActiveBehaviour" identifier 
"org.videolan.vlc" useActivationEventCode "activated" with stickyValue 
end tell

You can get detailed info on Remote Buddy's AppleScript interface by 
opening Script Editor's Library, then dragging Remote Buddy onto it. 
Each function is described in depth and commented sample code provided 
for each command.

Best regards, 
Felix