Heat 1 Tbsp. oil in a large skillet over high. Season pork chops on both sides with 1 1/2 tsp. salt. Cook pork until underside is golden brown, about 1 minute. Turn and cook on other side about 1 minute before turning again. Repeat, turning every minute, until chops are deep golden brown and an instant-read thermometer inserted into thickest part registers 135°F, 6–8 minutes total.

Transfer pork to a plate and let rest 5 minutes. Pour off and discard all but 1 Tbsp. fat from skillet. Add garlic to skillet, heat over medium, and cook, stirring, until fragrant and beginning to brown, about 1 minute. Add honey, red pepper flakes, and 1 Tbsp. vinegar and cook, stirring occasionally, until bubbling, about 1 minute. Remove from heat. Taste and add more red pepper flakes, if desired.

Working one at a time, return pork chop to skillet, spooning hot sauce over, making sure to thoroughly coat both sides. Transfer to plates or a platter. Add beans, black pepper, and remaining 2 Tbsp. oil, 1 Tbsp. plus 1 tsp. vinegar, and 1 tsp. salt to sauce in skillet. Cook over medium heat, stirring occasionally, until beans are warmed through, about 4 minutes.

Place escarole in a large bowl. Pour hot beans and sauce over escarole and toss to coat thoroughly and wilt escarole slightly. Serve alongside pork.