Page 6 details the method for searching for a code. It allows you to search forward or reverse, which I guess is a reference to the code numbers. It does not allow you to configure individual buttons so they will react differently to the way you press them.

Here is a link I found to a forum in French. Even after translating the page I couldn't understand all they said. Either you are the poster there or someone else is having the same problem.
[Link: translate.google.com]

I am afraid that the combination of Samsung having different codes and your remote either being older or not able to control the Samsung will not allow you to do what you want. Perhaps a new remote is in your future.