Great Valley is in Cattaraugus County, 2 counties west of Stueben County. Here's what I do know (cited) for Samuel Way Simmons:
Father: David P Simmons (1801-1872) I've hit a wall for his father, David Simmons, so I don't have any information about uncles.
Brothers: Bradley Simmons (b 1830-?), Seth Simmons (1831-1885), Josiah Simmons (1837-1862).
He also had a son, Samuel W Simmons (1857-1937) who lived & died in Cattaraugus County.
Seth Simmons (my g-g-grandfather), 1832-1885. He had a son, Seth, but I know he was institutionalized in a State Hospital, so there's another dead end for you.
If you know your Sam Simmons lived into the 1890's in PA, it doesn't look like anyone in this branch would work for you. As I continue my search for David Simmons' family, I will keep an eye out for you & post here if I find anything.
In your search, if you come across anything about David Simmons, please remember me! Thanks,