The Premier League leaders have taken maximum points so far in Group F and can guarantee a place in the knockout stages with a victory at the Stadio San Paolo.
Guardiola described Maurizio Sarri's Napoli as one of the best he has ever faced as a player or manager after City defeated them 2-1 in a closely fought tie at the Etihad Stadium earlier this month, and the Spaniard is expecting an even tougher contest in the return fixture.
"We need one more win to qualify, but we are going to the team that are leading Serie A and everybody knows the type of football they play in their own stadium, so it's going to be very difficult," Guardiola told a news conference.
"But it's a great opportunity for us to book our place and we're going to try our best to do it."
City travel to Naples after goals from Leroy Sane, Fernandinho and Raheem Sterling handed them a 3-2 win away to West Bromwich Albion in the Premier League on Saturday.
Sane's superb left-footed strike was his eighth goal of the season in all competitions, a return that has marked him out as a man Napoli are keen to keep a close watch on.
Napoli defender Elseid Hysaj was confident, however, of being able to deny the German winger.
"He is a strong player, technically and physically strong, and we will talk about him, but I have already studied how to stop him," the Albanian said on local radio.
Napoli were held at home by Inter Milan after the defeat in Manchester but have since beaten Genoa and Sassuolo in back-to-back Serie A fixtures to restore their fine form this season and open up a three-point lead at the top of the table.
"We've been good at reacting and playing our own game," Hysaj added. "We've been very mentally strong when we're losing games, even in Manchester we reacted and eventually we could even the tie."
(Reporting by Matt Westby; Editing by Christian Radnedge)
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