Brad Paisley's Latest Opry Show Helps Charity – and Maddie & Tae

Brad Paisley: Grand Ole Opry's Country Cares for St Jude Kids
Brad Paisley on the Opry stage in 2013
Rick Diamond/Getty

updated 09/25/2014 AT 12:30 PM EDT

originally published 09/24/2014 AT 02:00 PM EDT

Good music and a great cause were the themes of the night on Tuesday when Brad Paisley, Charlie Daniels, Randy Owen, Bill Anderson, Eric Paslay and Maddie & Tae gathered for the Grand Ole Opry's celebration of the 25th Anniversary of Country Cares for St. Jude Kids.

And for Paisley, it's these kinds of moments that matter most.

"It goes back to what Randy told me the day I met him, which was at St. Jude," recalled Paisley of his first encounter with Owen, who created the radiothon benefit back in 1989. "He said, 'Look, whatever awards you win, whatever accomplishments you rack up, they will pale in comparison to things like this. And you look back at the lives that you affected for the better, and the good things that you did will be the things you wish you'd done more of and the things you'll be the proudest of.' And he's right."

The most rocking moment of the night came courtesy of Paisley, who closed out the evening with tracks from his latest album Moonshine in the Trunk and a surprise "Old Alabama" duet with Owen.

But the most touching moment was when Charlie Daniels presented 9-year-old St. Jude patient Audrey Stanger with a signed guitar.

"I really want to learn [to play]," Stanger told PEOPLE, adding that it was "really scary" but also "pretty cool" to be on stage in front of the crowd. "I had no idea what was going on but [Daniels] brought me out and he signed it and he gave it to me and he wanted me to stay out for the next couple of songs."

It was a dreamy night for more than just Stanger and St. Jude, which received a portion of the proceeds from all ticket sales.

Duo Maddie & Tae, known for their anti-bro country anthem "Girl in a Country Song," celebrated their Opry debut and met one of their idols in the process.

The pair made a beeline for Paisley backstage, proclaiming, "We feel like we know you," and the headliner, in turn, made the girls' night. "I need to take you on the road with me," he told them. "We've got too much testosterone in country music."

"That was insane," Maddie Marlow told PEOPLE after the encounter. "It doesn't really feel real. To have one of our idols who we've listened to and bought music from since we were little enjoy our music is just nuts."

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