Scotland manager Craig Levein's full team for the friendly in Koper was revealed by the Scottish Football Association.
Jamie Mackie has been handed a start alongside Craig Mackail-Smith, who comes in as Kenny Miller is rested from the start.
Rangers goalkeeper Allan McGregor will start in goal with Mulgrew winning his first cap at left-back and Martin on the other side after Alan Hutton and Phil Bardsley pulled out with injuries.
Bristol City full-back Richard Foster was earlier called up as cover for the full-backs.
Caldwell and Christophe Berra form a familiar central defensive partnership with James McArthur, James Morrison and Charlie Adam in a creative midfield.
Mackie and Celtic winger James Forrest will start out wide with Mackail-Smith up front and Cardiff striker Miller on the bench following his exertions in the Carling Cup final on Sunday.
Meanwhile, Levein insists a "million things" have changed for the better since Scotland failed to qualify for this summer's European Championships in Poland and Ukraine.
Levein's first campaign as Scots boss ended in disappointment as yet again Scotland failed to make the finals of a major tournament.
"There are a million things that have changed," he said.
"I am 100 per cent happier now and better off with the group that I have got than I had back then.
"There is millions of stuff I didn't know.
"There was a little trepidation the last time round because I didn't know an awful lot about the international scene.
"Last time round I didn't know the players, I didn't know the best group, the best system to play but I am two years further down the road
"I am much more up to speed with the players I have available.
"I have increased the size of squad and the competition for places is really, really healthy.
"So of course, we are better prepared and we will be ready to go come September
"It puts me into a far better place, mentally, going into this qualifying campaign."
Mulgrew make his debut at the age of 25 and Levein insists it is simply a case of the Celtic defender maturing late in his career.
He said: "He would have been in my squad for the last game against Cyprus in November but he had an injury. I spoke to him and he was gutted.
"If you had said me to me two years ago that Charlie Mulgrew would be a starter for you at international football I would have said no, because in my mind, at that time, he wasn't.
"But he's just playing out of his skin. He has improved enormously, he is one of the players that I like.
"The penny has dropped in his mid-20s and he has improved enormously.
"So credit to Neil Lennon and Celtic for the faith in him and for the by himself for the faith in himself.
"I have had Paul Hartley and Barry Robson, to name two, who have taken their time but the penny has dropped and they have kicked on and the best part of their careers have been the latter part.
"I really take to them because they are trying to make up for lost time. Charlie is another one.
"So I am delighted for Charlie, it is a great honour for him.
"Everybody can improve at any age.
"It is a mental thing, a career thing, it is a decision that players maker to knuckle down, work hard, and do their best very single week and get any nonsense out of their head.
"It is hard to say what happens exactly but I have seen it happen on a regular basis."
With Manchester United midfielder Darren Fletcher absent through illness, and Cardiff City striker Kenny Miller rested, Wigan defender Caldwell will be captain, a fitting tribute to one of the great Scottish patriots, according to Levein.
He said: "He is captain material through his whole body," the former Scotland defender said.
"He is a proud, proud Scotsman.
"Every time he pulls on a Scottish jersey he is delighted.
"So it was important for me to recognise that."
Scotland team: McGregor, Martin, Caldwell, Berra, Mulgrew, McArthur, Forrest, Morrison, Adam, Mackie, Mackail-Smith.