The duo also met at the last year's championships when the Czech ninth seed came on top in another three-setter.
"She always makes it very hard for me," Kvitova said in her on-court interview.
"It's never easy to play the beginning of the tournament, especially here when I've been moved to the Centre Court, it's always a little bit different.
"But thank you roof, for holding it up for me today."
Paolini found some momentum and made Kvitova work in the second set but the experienced Czech comfortably took the third, firing eight aces and 36 winners throughout the match.
"I was trying hard in the second set to break her but this didn't happen. In the third I got an opportunity and I made it, and I think that since then I just kept going," Kvitova said.
"I was playing a little bit better, I was serving better as well. That was always the difference, probably.
"I was really happy with my serve, I didn't lose it today, so that's very positive," she added with a smile.
Kvitova will face the winner of unseeded pair Aliaksandra Sasnovich (29) or Nuria Parrizas-Diaz (31) in the second round.
