Prep the base: Add the sliced onion and bell pepper to the bottom of your slow cooker.
Sprinkle with a pinch of salt.
Mix the sauce: In a bowl, whisk together diced tomatoes, tomato paste, chicken broth, olive oil, lemon zest, lemon juice, garlic, oregano, basil, paprika, red pepper flakes, salt, and black pepper until smooth and combined.
Layer the chicken: Place the chicken thighs over the vegetables. Pour the sauce mixture over the top, making sure the chicken is mostly covered.
Add olives and capers: Scatter the Kalamata olives, green olives, and capers over everything.
Cook low and slow: Cover and cook on Low for 5 to 6 hours, or on High for 2.5 to 3.5 hours, until the chicken is very tender and easily pulls apart.
Adjust seasoning: Taste the sauce and add more salt, pepper, or lemon juice if needed. If you want a thicker sauce, remove the lid for the last 20 to 30 minutes or stir in a slurry made from 1 teaspoon cornstarch and 1 tablespoon water, then cook 10 more minutes.
Finish and serve: Shred or slice the chicken into large chunks.
Stir back into the sauce. Garnish with fresh parsley or basil. Serve over couscous, orzo, rice, or alongside crusty bread to soak up the juices.