As reported earlier by AFL.com.au, Phil Davis and Callan Ward have retained their positions as co-captains, with new signing Shaw joining Tom Scully as their deputies.
Shane Mumford and Stephen Gilham round out the leadership group.
Shaw struggled with some on- and off-field issues during his decade at Collingwood, capped by an undisciplined display in the Pies' elimination final loss to Port Adelaide, his final game for the club.
It led some to query the merits of him joining GWS and its fledgling list, but the 28-year-old has proven an outstanding influence to date, Davis said.
"I don't know what the media in Melbourne think about Heath, because they always seem to be on his back, but he's been unbelievable," he told AFL.com.au.
"What they thought he was going to provide has been nowhere near what he's actually been able to do.
"He's been enormous for our footy club and he's just a natural leader, people are drawn to him, he's an infectious character, he leads by example and sets good standards."
Shaw has settled in well in his new city, recently moving out with young teammates Stephen Coniglio and Jonathon Patton, having initially lived with brother Rhyce when he first made the move from Melbourne.
He was keen from the outset to be part of the leadership group, but says the vice-captaincy came as a surprise.
"I assumed a bit of a leadership role straight away, being an older statesman and a bit more experienced with the group," Shaw said.
"I thought going into the leadership group would be the right move.
"I obviously didn't expect anything more than that and to be named as a vice-captain is pretty exciting and something I've never held before.
"I've been in leadership groups before but I've never been a vice-captain, so it's the icing on the cake.
"It's exciting times ahead."
Ward and Davis, who are both 23, will now move into a third year captaining the AFL's youngest club.
Originally named co-captains alongside Luke Power back in 2012, they took over the position themselves last season and will continue to lead the way for the third-year franchise.
While they have proven astute choices, Ward admits he wasn't sure which way the club would go with its captaincy, particularly considering the resumes of some of the new recruits.
"I was definitely hopeful. I didn't know what they'd do," he said.
"I knew with all these guys and their experience they'd be pushing up towards leadership positions as well.
"It's great to have Heath and Shane and Stephen (Gilham) up there as well and I know they're going to help me and Phil out."
Key defender Davis was the only GIANT to play every game in the club's inaugural season, but spent nine weeks on the sideline last year with a back injury.
Fully fit and with a significant lift in experience alongside him in the backline, Davis is hopeful the club can start to enjoy some more on-field success.
"It's a great honour to lead this footy club and it's something that I'm very proud of now, but it's something that when I finish my career in 10 or so years I'll be even more proud of it," he said.
"It's been a challenging role but one I'm slowly improving at and I've had a lot of help along the way.
"Callan has been great to bounce ideas off and work with and I'm thrilled to do it again and hopefully this year we can have some more success and make everyone's life a bit easier."
