Season roast liberally with onion powder, garlic powder, salt, and pepper on all sides.

Heat a pan over medium-high heat until scorching hot. Add olive oil. Sear beef until brown on all sides, holding up roast to get all edges, 5 to 10 minutes. Transfer roast to the slow cooker. Deglaze the pan by pouring in broth and scraping up browned bits. Add Worcestershire sauce. Pour mixture over the roast in the slow cooker.

Add tomatoes, pepperoncini peppers and their juice, garlic, and Italian seasoning to the slow cooker. Turn roast over a few times to coat. Cover slow cooker and cook on High for 4 hours.

Add bell peppers and onion to the slow cooker, tossing to incorporate. Continue cooking on High for 1 more hour.

Shred beef and season with salt and pepper to taste. Let beef and sauce sit in the slow cooker on Warm until ready to serve.

Meanwhile, toast hoagie rolls, if desired. Top rolls with shredded beef and add provolone cheese to each.