On the iPhone, hit phone, then missed calls or recents, then hit the circled i to the right. Scroll down to where it says 'Block Caller'
On the Android, there is also a block caller when you hit phone.
On the Android (Samsung specifically), open Phone; got to RECENT; press # you want to block until the menu comes up; select "move to reject list" and there it is. Do the same if to remove from the reject list if you accidentally chose a different number.