The Wigan defender has been named captain in the absence of Darren Fletcher after manager Craig Levein decided to rest Kenny Miller from the start.
Caldwell will win his 47th cap in the international in Koper.
Gary Caldwell: "I've never started the game as captain," he said. "Obviously Fletch is the captain and Kenny is the vice-captain so it is an honour to get it, but they are obviously the men in possession and I am 100 per cent behind them.
"But to get it for one night will be special."