I think I have a similar problem with that reported. I have a Samsung SmartTV UN40ES6100G and I am unable to configure the discretes IR codes. The TV manual has no information and honestly do not know what to do.
Have control called Amulet and it can record TV of the original control keys on it. But the Amulet has more keys than the control of the TV. For this reason, I have sought a way to can record other commands in Amulet.
I bought a universal remote control but failed. The only command that could identify was the skipminus.
I wish I could solve this problem. I do not know if there is in control of Samsung some combination of keys which can trigger other commands.
I thought about buying a MCE IR Blaster device but do not know if this is the correct path.
If anyone can help me with this issue would be great because I'm already many days trying to find some solution to no avail.