He could meet his grandparents. Meeting them would give him a deeper understanding of his family history and the roots of the Winchester family's connection to the supernatural. Another interesting character would be young John Winchester. Sam could see what his father was like before all the tragedies happened and maybe even influence him in a positive way.
Sam could meet an ancient prophet from a time long before his own. This prophet might have foreseen Sam's time - traveling adventure and have some crucial information for him. He could also run into a group of knights who were secretly fighting supernatural creatures in the Middle Ages. Sam could learn from their combat techniques against the supernatural and they could be amazed by his modern - day knowledge and weapons.
He could meet Dr. Halsey when she was just starting her research on the Spartan program. Master Chief could give her some insights from the future, which might change the way the program is developed.
She could meet her younger self. This would be an interesting encounter as she could offer advice and guidance to her younger version. Maybe she could help her younger self to be less afraid of her powers.
He could meet Peggy Carter. Since he had a strong connection with her in the past, it would be a very emotional reunion. They might share some unspoken feelings that were left unexpressed before.
One plot idea could be Sam going back in time to prevent a major tragedy in his family's past. For example, he could try to stop the demon from killing Mary Winchester, which would change the entire course of his and Dean's lives. Another idea is that he goes back to a time when hunters were just starting to organize and he tries to influence the development of the hunting community for the better.
He could meet historical figures like Julius Caesar. Nero might have a conversation with him and learn about ancient Roman politics.
He could meet his past self. It would be really interesting to see how he interacts with his younger, more naive self. He might try to give advice to his past self, like how to better control his power or avoid certain dangerous situations.
She could also encounter characters who were once enemies but are now in a different situation due to the time travel. For instance, she might come across a young Death Eater who hasn't fully committed to the dark side yet. Ginny could try to change their path and prevent them from becoming evil in the future.
He could meet his past allies in a different context. For instance, he might encounter Kakyoin or Polnareff when they were just starting their journey. Maybe he could also run into Dio at a time when Dio was still plotting his rise to power, which would create a very tense situation.
Lucy may also come across ancient warriors. For example, she could meet a Spartan soldier and be amazed by his combat skills and strict discipline. They could have a brief encounter where the Spartan is curious about this strange girl from another time.
There's a possibility that Zuko would meet his grandfather. His grandfather's actions and decisions might have influenced the path the Fire Nation took towards war. By meeting him, Zuko could try to sway his grandfather's views and change the future of the Fire Nation at its root.