AutoHotkey has the ability to send keystrokes in a variety of different ways (SendRaw / SendInput / SendPlay / SendEvent). I'm not quite sure what approach the simple key::key mapping uses, but it must be one of them. My guess is that one of SendRaw, SendInput, SendPlay, or SendEvent will work the same as key::key.
Also #IfWinActive sometimes doesn't work exactly the way you expect, especially with fullscreen games. So I usually test my AHK scripts without the #IfWinActive to make sure they're working correctly. Once it's working, I introduce the conditional.
UPDATE
From http://www.autohotkey.com/docs/misc/Remap.htm:
When a script is launched, each remapping is translated into a pair of
hotkeys. For example, a script containing a::b actually contains the
following two hotkeys instead:
*a::
SetKeyDelay -1 ; If the destination key is a mouse button, SetMouseDelay is used instead.
Send {Blind}{b DownTemp} ; DownTemp is like Down except that other Send commands in the script won't assume "b" should stay down during their Send.
return
*a up::
SetKeyDelay -1 ; See note below for why press-duration is not specified with either of these SetKeyDelays. If the destination key is a mouse button, SetMouseDelay is used instead.
Send {Blind}{b Up}
return
My notes:
I suspect the reason a::b is working but a::Send b is not is because of how a::b breaks button down and button up handlers into two separate mappings. The game's gameloop probably polls the gameplay keys for "keydown" state, which would not be maintained consistently if AHK is synthesizing repeats. Remapping a_down->b_down and a_up->b_up probably makes AHK emulate more accurately the act of holding the key down, which may matter for programs which test for key state in particular ways (GetAsyncKeyState?).
The asterisk in the mapping means "Fire the hotkey even if extra modifiers are being held down."