/dev/ttyACM0/dev/ttyACM0 is a USB CDC/communication device (CDC) of sub-type "abstract control model" (ACM device). That is what the Arduino is.
/dev/ttyS0/dev/ttyS0 is a hardware serial port - the (typically) 9-pin D connector on the back of your computer.
If you want to use /dev/ttyS0/dev/ttyS0 (why would you?!) you will require a special cable that converts the RS-232 voltage signals from the 9-pin D connector into the right TTL level signals for the Ardiuno and wire it in to the right pins on the board.