You could, although the layout would be awkward - and I'd probably put it on P2 instead. Just remember that the P1 & P2 buttons are your save buttons in programming mode as well, so don't know if this would cause a problem. You COULD always just tie both s1 & s2 inputs to the same button, then they would do both options at once. Wouldn't matter in games like Xevious as you have unlimited bombs, but you'd run out of warps right away in Moon Cresta and don't know how the fast/slow in Qix would be affected.
I've added a 2nd button to these games before, and they look fine as long as you match the original button in color. If it bothers you that much, do one of two things, either add a floor pedal for the 2nd button that you can stick inside the coin door when you're not using it, or don't play any of the 2 button games. There's only 5 or so anyway....