When you use it with the terminal, qvm-sync-appmenus, like you did in the picture, then you'll need to have the TemplateVM started beforehand. It won't start on its own. Once its fully booted, then run the dom0 command again.
There is also a graphical method, there should be a VM Settings, next to the "Start" in the menu's that you mentioned. If you can find the VM Settings, then you can go to the Applications tab, and then click on the "Refresh Applications" button at the top of the window. This will automatically start the Template the AppVM is based on, execute the sync commands, and then automatically shut down again. You'll have to wait till its done and closed itself before trying to manage any of its menu or shortcuts.
I'm sure you know, but just in case, remember to restart any AppVM's that is based on the template.