A:Answer I don't have a Samsung Smart TV, but the top buttons are customizable to a limit. They are designed for activities, for example; "Watch a movie" can be setup so that pushing that button will turn on your TV, your Sound System, your Blu-ray player, and change the inputs for you automatically. You can also customize the LCD menu, as well as make each button below that perform a different function for each independent device.
If you do program the remote to do this, be sure to select the device you are trying to control via the LCD screen. Once you select your device, the remote will automatically change the buttons based on how you customized it. Meaning with a little tweaking in the Logitech program, you can accomplish your goal of using one button to perform two different functions on separate devices. (Without having both the Hub and DTV Guide coming up at the same time)