I would take 25 from Greenville to Hendersonville - stop downtown ( shops and restaurants)..then I-26 to I-40 in Asheville ( you'll pass a sign for the NC Arboretum- nice stop). I'd take 40 east to U.S. 221 north through Marion and on to Boone - lots of nice scenery but it's a slow drive - mountains.
I tell you - for a picnic in that area I'd suggest getting on Highway 64 in H'ville and go west about half an hour to Brevard...lots of beautiful picnic spots along the waterfall road to the Cradle of Forestry ( google it). Or - you could visit one of the apple orchards in the area ( such as J.H. Stepps) and picnic there.
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