Nestor, 40, teamed up with 22-year-old Pospisil for the doubles rubber in Canada's first round tie against Spain two months ago and went up 2-1 after three sets against second-ranked doubles duo Marcel Granollers and Marc Lopez. But the Canadians imploded in the fourth and fifth set, winning just five games.
It was the third straight doubles defeat for Canada in Davis Cup play, with Nestor and Pospisil capturing their nation’s last doubles triumph in a World Group play-off in Israel in September 2011.
The recent string of doubles defeats is not a major concern for Nestor, a 21-year Davis Cup veteran.
"Well I think we're playing fine," Nestor said. "Against Spain we had some chances maybe to win that match a bit earlier, perhaps in the fourth set.
"I think we're not meant to be worried about the way we're playing, plus we're playing on our home court so if we play well we should have a good chance."
Nestor, who is ranked sixth in the world in doubles, also shed some light on the late-match fade-out against Spain. He said he "hit a wall" while it was already known that Pospisil was recuperating from a bout of mononucleosis.
"Playing matches on Tour, you're playing one-hour matches then all of a sudden you're going into matches that get close to four hours and are pretty physical, so I just kind of hit a wall and just didn't feel that good on the court towards the end of the fourth and fifth set," the Toronto native said.
Vancouver's Pospisil will be aiming to once again feed off the energy generated by playing in his hometown and said preparation for Italy won't be any different despite the Spain defeat.
"For sure we'd like to bounce back," he said. "Any time you lose in a Davis Cup, you want to bounce back the next tie. As Daniel said, the last time we played very well, we gave ourselves a chance to win and for reasons out of our control we weren't able to get the win, but we played very well.
"So we're not going to change anything in our preparation, we're going to go in with the same mentality and if we put up the same performance I think we'll have a good chance to win."
Considering Canada's recent double woes it will take a significant effort to stop the losing skid, with Italy expected to name the world No. 3 duo of Bolelli and Fabio Fognini for Saturday's rubber.
However, Bolelli had to withdraw from his second round tie against Bulgarian Grigor Dimitrov at the Sony Open in Miami on March 23 with a wrist injury, and is still not a certainty to play.
"My wrist at the moment is getting better," Bolelli said during what was an animated Italy press conference. "My condition is better day-by-day so I'll just wait until Thursday or Friday to see if I'm able to play or not.
"But right now, my wrist is getting better and I'm confident (of playing)."
Should Bolelli miss out, Italy will replace him with 25th-ranked doubles player Daniele Bracciali, who teamed up with Fognini at an ATP event in Casablanca last year and reached the final.
Fognini and Bolelli faced Nestor and India's Mahesh Bhupathi — who were seeded fifth — in the third round of this year's Australian Open doubles tournament, with the unseeded Italians winning in three sets on their way to the semi-final.
But Fognini showed plenty of respect for his Canadian rival.
"He's won everything so he's one of the best players in the world in doubles," he said. "He played really good the last time we beat him in Australia, but conditions here are completely different, we will see on Saturday."