Williams was handed the armband on the afternoon she became England's most capped player, surpassing Rachel Yankey's total of 129 appearances.
And though a goal eluded the Liverpool Ladies midfielder at Hartlepool's Victoria Park, strikes from Karen Carney (2), Fran Kirby and Lianne Sanderson ensured the contest delivered on substance as well as sentiment.
England had won only one of their previous 14 meetings with the Swedes - ranked three places higher than Mark Sampson's side at fifth in the world - but they will head to Cardiff for a World Cup qualifier against Wales later this month in confident mood after a dominant display.
Kirby's debut might have been more eye-catching still had she connected better with a ball that bounced invitingly on the edge of the box with just minutes gone, while Hedvig Lindahl - celebrating her own milestone of 100 Sweden caps - needed to save smartly from Jodie Taylor.
Karen Bardsley tipped a threatening Lotta Schlein cross onto the crossbar at the other end but Sampson's side saw prolonged pressure finally count 11 minutes from the break, Carney afforded a second chance after her spot-kick hit the post.
The Birmingham winger went close to a second but it was Kirby who doubled England's advantage seven minutes after the restart, a curling left-footed shot from range rich reward.
She departed on the hour to a standing ovation and replacement Eni Aluko came close to making a swift impact herself, thwarted by the crossbar.
But Sanderson tapped in on 67 minutes to further extend England's lead and Carney found the top corner 10 minutes from time to consign Sweden to their heaviest defeat in two years.
Sampson's side are next in action at the Cardiff City Stadium on 21 August, needing only a point against Wales to book their place at the 2015 World Cup finals in Canada.