You were right about pressing the buttons in order that fixed my issue there.
I tried the start game in fullscreen but it won't move it to the 2nd monitor. It will only move it if I have it in windowed mode. I also have the Exit RCPS3 when process finishes checked. If I could find a way to replace WinMaximize to make it full screen that problem would be solved.
This is the script I put together. I finally found out that I needed to change the sleep time to 6 seconds to give it enough time to load in Bigbox because for some reason Bigbox is much slower at launching games.
#NoEnv
Sleep, 6000 ;wait 6 seconds
Send #+{Right} ;Send Win+Shift+Right
Sleep, 1000 ;wait 1
WinActive("A") ;grab the currently active window
WinMaximize ;maximize the currently active window
Return
$ESC::
{
SetTitleMatchMode, 2
WinWaitActive, RPCS3
Send !{f4}
}