The pair will appear in the May 7 episode of the show, which is wrapping up its second season.
"Rayna organizes a charity concert at Fort Campbell after finding out Luke has been injured in Afghanistan, forcing him to cut his tour short," an ABC synopsis said. "Deacon and Maddie are brought closer together as they chart a new course for their future. Teddy is beginning to feel like his family is slipping further and further away from him. Juliette is racked with guilt knowing that her back is against the wall after Jeff threatens to go to Avery with the truth. Gunnar is feeling pressure to reveal a secret about Juliette to Avery until Zoey urges him that his professional and private life should be kept separate. And Will and Layla begin shooting their new reality series."
Nashville stars Connie Britton as fading country music legend Rayna Jaymes and Hayden Panettiere as her rival Juliette Barnes. The ensemble also includes Eric Close as Teddy Conrad, Charles Esten as Deacon Claybourne, Clare Bowen as Scarlett O'Connor, Jonathan Jackson as Avery Barkley, Sam Palladio as Gunnar Scott, Chris Carmack as Will Lexington, Maisy Stella as Daphne Conrad and Lennon Stella as Maddie Conrad.
Guest starring in the episode along with Obama and Pickler will be Chaley Rose as Zoey, Oliver Hudson as Jeff Fordham, Aubrey Peeples as Layla, Ed Amatrudo as Glenn Goodman, David Alford as Bucky Dawes, Melvin Ray Kearney II as Bo, Will Chase as Luke Wheeler, Kourtney Hansen as Emily, Briana Venskus as Gina Romano and Jason Alan Smith as Colonel Stephen Mason.