The versatile Euro 2022 hero - who had been deployed as a left-back last summer - rose highest either side of Sofia Cantore's controversial equaliser to extend the Lionesses' unbeaten run under Sarina Wiegman to a whopping 27 games.
Wiegman did not shy away from significant alterations from the team that demolished South Korea on Thursday, making nine changes in total as only Jess Carter and Alex Greenwood held their places.
An unfamiliar England side conceded the first chance of the contest to Italy in the fifth minute, as Aurora Galli drove forward on the break and picked out Valentina Giacinti, whose strike was saved well at her near post by Ellie Roebuck.
Italy were living dangerously at the back, though, and a pair of errors in the seventh and eighth minute handed Daly two opportunities to let fly, but Azzurre goalkeeper Laura Giuliani was equal to both attempts.
Following that brief period of instability, Italy's low block was proving effective in frustrating England, whose returning difference-maker Keira Walsh was largely unable to influence the game in the early exchanges.
However, the Lionesses would take a deserved lead with 33 minutes gone, as Katie Robinson's cross from the right was on the money for Daly, who rose highest to head home.
The versatile Daly headed against the bar just before the break too, although the offside flag soon went up against the threatening Aston Villa star.
Wiegman refreshed her midfield at half time with the introductions of Jordan Nobbs and Katie Zelem - taking off Walsh and full debutant Jess Park - and Nobbs would immediately force the issue with two shots in quick succession.
The ex-Arsenal midfielder blasted a close-range effort into the body of Giuliana in the 54th minute before stinging the palms of the Italy goalkeeper just one minute later, as the Lionesses pressed for the insurance goal.
England's inability to kill the game off would haunt them, though, as in the 62nd minute, Italy attacked down the left through Barbara Bonansea, who crossed for Cantore to send a tame header towards goal, but Roebuck flapped at her attempt and could only help the ball on its way over the line.
Greenwood's goal-line clearance came just a split-second too late, and there was a debate to be had over whether Bonanasea managed to keep the ball in play, but the goal was given.
Italy's reprieve would last a mere nine minutes, though, as Daly harnessed her aerial ability once again to restore England's lead, meeting a floated cross from Lauren James and directing a brilliant header across goal into the far corner.
Despite a couple of nervy moments at the back in the final exchanges, the Lionesses held on to move onto six points from their two games, and they will finish their Arnold Clark Cup campaign against Belgium at Bristol City's Ashton Gate on Wednesday.