Xylina McDaniel added 15 points for the Tar Heels (13-3, 1-1 Atlantic Coast Conference), who used a 24-2 run late in the first half to take control after an early 10-point deficit.
Jessica Washington added 10 points to give Carolina three players in double figures.
UNC led 45-29 at halftime and by double figures for most of the second half, though the Wolfpack (14-2, 1-1) rallied to within five points three times in the final 3 minutes only to fall short.
Markeisha Gatling had 18 points to lead N.C. State, which had its first national ranking since the 2006-07 season under late Hall of Famer Kay Yow. First-year coach Wes Moore's team was trying for its first 2-0 ACC start since 2000.
The Tar Heels shot 51 percent, with DeShields scoring 10 points during UNC's big run. She came up with a season-high nine rebounds and four assists to go with her 21 points.
Carolina improved to 9-1 in the last 10 meetings against the Wolfpack in Chapel Hill and 52-45 all-time against its Triangle foe.
The Tar Heels hit the road Sunday for its third-straight game against a top 25 opponent when they take on #18/17 Florida State at 1 p.m. on the Regional Sports Network and ESPN3.