All the answers you received are great. From your MC's POV when he first sees someone with seven fingers, you could just say: The Main Character watched the man close the distance between them. When he was close enough, the MC noticed the man's hands. No, not an Earth human but a Tzor alien, the MC realized. Tzors looked like Earth humans and only the 2 extra fingers on each hand showed their true nature. Which, after their planet Tzor was destroyed with a nuclear bomb, made them blend in with humans far easier. The Tzor raised one hand and closed the three middle fingers in the traditional greeting of his people.
See how short this is. But we know several things: that Tzors lost their planet, they look like humans, have seven fingers, live with humans and have a gesture all their own. You don't need to write a whole chapter just to show them and their seven fingers. Narrate the points when the need arises during the novel and let the flow of the story guide you.
Edit: Michael Richardson, you're right. I didn't understand it. My bad. I apologize. But I don't think it's as hard as you say. If the author starts describing the new character like he would describe a normal one, and keep with the details throughout the story, it will appear normal to the readers in the end. Maybe (I'm going to keep Tzor): The MC watched his friend, Tzor, approach. He waved at him in the gesture they had used since they were kids, with the first three fingers closed and the seventh one slightly bent. Tzor would understand it. He was more like a brother to him. They were born on the same day and had lived next to each other all their lives.
Tzor used the same gesture to wave back with not just one, but three arms. The MC grinned. He was relieved to see his seven foot, green haired friend back safe from war and his usual funny self.
Continuing along the same vein through the whole story, won't make the characters sound abnormal with 6 arms and seven fingers.