Well...since Nami, Chopper and Jinbei has been able to hold their grounds against Big Mom in the past, I think Luffy feels that they can hold their grounds again.
As for Akainu comparison, I don't think it works like that. Remember, among all villains, Akainu is the only one who mentally broke him. So, obviously he would be more cautious. Nevertheless, Luffy was still fine with Zoro fighting a fellow Admiral Fujitora.
But still, at the end it doesn't matter. This is Shonen and so the MC will be made to go up against the primary villain i.e. Kaido and not secondary villain i.e. Big Mom. That's just how it is.