SPI across two Arduino DUE's

Does your application involve devices mounted on the same board or are this communication between two systems? I ask because I think that SPI communications are typically between a master and slave in the same system, if not on the same PCB then on a daughter card or similar.

For communication between systems using a UART or USART might be more useful. And in that case there is no concept of master and slave so symmetric libraries can be used on both sides.

If you must use the SPI bus I suggest digging into the initialization code so you can see how the master is set up and that should give you some hints on how to configure the slave. You will also likely have to study the data sheet to understand how the SPI port is programmed and write your own slave driver. It maybe that some of the code from the library can be copied and modified as necessary to make a slave driver. (no pun intended!)