Combine the tequila and jalapeño in a jar, shake to combine, and let sit at room temperature (preferably in a dark place) for 6 – 24 hours. The longer it sits, the spicier it will get. Strain the tequila through a fine mesh strainer and discard the jalapeño and seeds. You can make a lot and keep it refrigerated for up to a year if in a covered jar or bottle.
Drain the juice from the pineapple, saving ¼ cup of the juice. Reserve 1 pineapple ring for garnish, if desired.
In a blender, combine the strained tequila, the pineapple rings, ¼ cup reserved pineapple juice, the lime juice, agave, Cointreau, and ice. Blend well.
If desired, you can rim your serving glasses with chili salt. Simply combine the salt and chili powder in a small plate or saucer. Run a lime wedge around the top of the glass, place in the chili salt and wiggle it around to coat. Can be coated ahead of time.
Garnish the margaritas with a quarter of a pineapple ring and a slice of jalapeño, if desired.