Okay, Seary reference for Jolliffe in Newfoundland, in case it helps:
Early instances: Elijah Jollieff, proprietor and occupier of fishing room at Old Perlican, Winter 1800-01 (Trinity Bay census); Peter Jolliff, Jr., merchant of Placentia Bay, 1804 (d'Alberti papers vol 14); James, planter of Fogo, 1816 (MUN history); James Joliffe, planter of Joe Batt's Arm, 1821 (soc. propogation of the gospel records).
There are a few later references but those are probably the ones of interest. The communities are all over the map. The only ones somewhat near Nathanial Smith of Greenspond are the two James' - Fogo and Joe Batt's Arm are both on Fogo Island, which is not too far from Greenspond.
Your Smith might have worked as part of the migratory fishery, fishing in Newfoundland for a few seasons, but never settling permanently.
J.