Xpadders equivalent of Saiteks Shift key function is the set feature. But the set feature is even better, you can use up to 8 sets and you can make any button to such an shift button.
You use only the first set at the beginning and you can select any set by clicking on it's number on the lower right of Xpadders main window. You need that to configure the second or else set.
To switch between them with your controller you need to assign this to any button.
Click on the joystick button, you want to use as these shift button. Click on "Advanced" and then on the left side on "Set Selector".

Here you can assign to which and how this button should switch to another set.
"one way" means that Xpadder will switch to this set when you tap the button, but you cannot get back by pressing it again.
So "two way" means the same, but you an switch back by tapping it again.
And "while held" means that Xpadder will switch to this set while you hold this button and switches automatically back when you release it.