Here is a screenshot of what you're looking for.
To get here go to my computer and right click. Select properties then advanced system settings then environmental variables. You want to set the path in the User variables, not in the system variables. Path variables take the form of:
path;
So your path variable looks something like path1;path2;path3;path4;
Let's say the program you're trying to run is located at :
C:\program files\my-program\someprogram.exe
You would add the following to the User Path variable:
C:\program files\my-program;
If you wanted to run it from the CMD prompt you would just type the name of the program which in this case is someprogram. Furthermore, if you don't like typing the full name of the file each time into the CMD prompt you can bind the exe to a shorter name. I don't recall how to do that but you should be able to find it with a little googling.