Arsène Wenger goes into a riveting Champions League fixture against the Italian high-fliers Napoli with the confession that he is obsessed by an ambition to win the tournament. He sees it as a glaring hole in his managerial record. "It is something I miss," he says. "I will try to fight very hard to fill my CV with that. But you play against Barcelona, Bayern, Real Madrid – every year they are there with a chance. Every year you always think: 'Let's do it', and one year it will go for you. Let's hope it will be this year."

He is about to be reacquainted with Rafael Benítez, one of only four managers in this season's edition of the Champions League to have previously won the competition, as have Carlo Ancelotti, José Mourinho and Pep Guardiola.

Benítez, returning to London so soon after that strangely uncomfortable spell at Chelsea, arrived for pre-match training at the Emirates Stadium radiating contented confidence. In fact, after a scintillating start to his Neapolitan adventure, he is having to tone down the levels of expectation. Before their opening Champions League fixture, against Borussia Dortmund, Benítez gave a rallying call, urging his club to show the world how strong they are. Now, the message has changed. "We probably need to control the euphoria," he said.

He is happily settled in southern Italy. "It's a nice place, nice fans with a lot of commitment. It's very similar to Liverpool in the passion for the team and the enjoyment of football. You see it everywhere. That's why it has been easy for me."

The job description at Napoli was a challenging one. Effectively Benítez has been asked to take a team who have been enjoying their best football in decades, with a thrilling Champions League run and Serie A runners-up spot in the past two seasons, sell the most potent weapon and make the side better.

There was some scepticism, largely based on Benítez's previous encounter in Serie A. Picking up Mourinho's baton in 2010, he arrived at Internazionale to work with a team who had just won the treble, an extraordinary peak for a group with considerable age and experience on its side. Benítez's spell with Inter turned out to be disappointing.

Wenger believes Napoli are an entirely different proposition. "I'm not surprised Rafa is doing well," said the Arsenal manager. "Maybe his first experience in Italy he took a team who had been at a high and they were just over the hill, so that was a bit of a gamble. Napoli are on the way up. He can give them more experience and quality."

Arsenal's Arsène Wenger, right, arrives for training with his star signing Mesut Özil as they prepare for Napoli's Champions League visit. Photograph: Eddie Keogh/Reuters

In keeping with the mutual appreciation society that comes naturally to two coaches who always got along well, Benítez was also wholehearted in his praise of Wenger. "I think Arsène Wenger is the best coach in the Premier League," said the Spaniard. (No mention of Mourinho considered necessary.)

Napoli are a substantially changed side to the team who finished second in Serie A last May. There have been major structural changes, with a new coach, goalkeeper, centre-half, centre-forward and tactical approach among the most significant shifts. There is a notable Hispanic flavour with three players arriving from Real Madrid's books (the defender Raúl Albiol and striker José Callejón accompanying the grandstand signing of Gonzalo Higuaín) and the Spanish goalkeeper Pepe Reina arriving on loan from Liverpool.

With Callejón and the vibrant talent of the local boy Lorenzo Insigne on either side of Higuaín, supported by the assists of Marek Hamsik, a new-look front-line Wenger regards as "dangerous" has been built in the aftermath of Edinson Cavani's expensive departure to PSG.

Insigne sums up the new spirit in the camp: "So far everything is beautiful. But we must remain humble and follow the Benítez way. I like the style. We play with the ball on the floor and this gives us confidence. Benítez has given us a winning mentality and with pleasure I sacrifice myself to contribute defensively."

Napoli play bright, fast, breakaway football and their start to the campaign has been almost flawless. They have won five of their opening six league games and were buoyant to triumph in their European opener against Dortmund.

The contest is set up intriguingly because Benítez identifies Arsenal's ball possession as their strength, and Wenger points to counterattacking as Napoli's greatest asset.

Arsenal feel an extra pressure to do well in this game because they are up against Dortmund in what Wenger describes as a "double confrontation" next, while Benítez will be looking to push on against what would appear to be the weakest member of the Group F quartet, Marseille.

Friendship will be put to one side as these two wily coaches try to make ground in this complicated group. Benítez empathised with Wenger's ongoing obsession to become a Champions League winner after so many tries. "He's a great manager, great person, always top-four doing a great job. Hopefully he can win. But another year," he grinned. "Not this one."