Heat grill to low to moderate heat or set oven control to broil. Spray rack or broiler pan with nonstick cooking spray. Place peppers on grill or rack in broiler pan. Grill peppers 4 to 5 inches from heat about 4 minutes, turning several times, until skin is blistered and charred. Place peppers in paper bag. Close tightly; let stand 15 minutes.
Mix tomato paste, water, vinegar, Worcestershire sauce, mustard and thyme; set aside. Remove peppers from bag. Peel off skin; discard. Keep peppers warm.
Trim excess fat from pork chops. Slash outer edge of fat on pork 1/4-inch deep to prevent curling. Rub both sides of pork with Cajun seasoning blend. Place pork on rack or broiler pan. Grill pork 4 to 5 inches from heat 4 minutes or until seasoning browns; brush with tomato sauce. Grill 1 minute; turn. Grill 3 minutes longer; brush with sauce. Grill 1 to 2 minutes longer. Heat remaining sauce to boiling; serve over pork and peppers.