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If pork roast shoulder is frozen, put in the fridge to defrost 2-3 days before cooking. Trim off any large sections of fat and discard.
In a small bowl, combine 2 tablespoons of the brown sugar, smoked paprika, salt, pepper, and garlic powder. Rub the mixture all over pork until it's soaked in and evenly coated.
Place onions in a layer on the bottom of slow cooker, place pork shoulder on top.
In a small bowl, stir together remaining ingredients from apple cider vinegar to ground mustard, plus the leftover tablespoon of brown sugar. Gently pour the liquid over roast. You should have about 2 inches of liquid on the bottom; if not add a bit of stock or water.
Cook covered on LOW for 8–10 hours or HIGH for 4 hours until pulled pork is fork tender. Important: Do not discard liquid after cooking.
Use a fork to shred the meat in the slow cooker or on a plate. Toss shredded pork with the liquid until well coated. Slow cook on HIGH for 15 minutes more to infuse flavors.
Use tongs or a slotted spoon to serve as desired, or use it to make my slow cooker Pulled Pork Sliders.