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What you are describing sounds like the 'shortcuts' that are defined for menus, not the keyboard shortcuts managed in Preferences.
There are 2 types of keyboard shortcuts in use.
One is the letters used in menus. On Linux and possibly Windows (but I don't think MAC), you can press the Alt key plus the underlined letter in a menu name to open the menu (e.g Alt+F for the F in File). You can then press a letter on the keyboard (without Alt) corresponding to the underlined letter in a menu item (e.g. N for New).
But the more common usage of shortcuts are the ones you see usually to the right of the menu entries, like F5 or Ctrl+N. For these keys you just press what they are. You can change or remove them in Preferences->Keyboard Shortcuts.
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