Great

Here's a basic step-by-step to get you started..
(Also, check out the "Layouts_demo.pcr" etc. in the Examples folder)
Now that you have the remote working and the "ATI Remote Wonder.pcr" open on PCRC it goes like this:
(Using VLC media player in this example..)
1. Open the software you're going to create a new layout for (VLC media player)
2. in PCRC open the "Actual layout" dialog
3. In the Running applications list you should see VLC media player; wxWindowClassNR, highlight that and click the "Add to layouts" button ..and Accept the addition
4. Back in the PCRC main screen select VLC media player (or whatever you possibly named the layout entry) from the list of Actual layouts
5. On the Execute action area select New (action) and name the new action (ie. Play/Pause)
6. Activate the Play button on the Remote commands list by clicking the command or by pushing the play button on the ATI remote
7. Drag the Play command from the remote commands list to the Trigger commands box (or CTRL+A - or left click and select "Copy to action trigger list)
8. Select the Actions list dialog and click on New...
9. From details select "Particular key(s):" and type in the needed key, in this case Space (er.., you wanted Q ..so just type in Q)
10. Accept, save and Run! to test the setup!
11. Repeat steps 5-9 as needed.........
If you have problems even though the right program is active, try different Destination window options. Also, the Running applications list is a good place to experiment in case of trouble ..the program relies on the Window titles and/or program class names and while this makes the software really versatile and powerful it's also a weakness as with some programs determining the right destination window(s) etc. could be a real PITA. (Essentially programs that are internally divided to many "windows/classes/whatever".
Anyway, this should get you started..