Jessie Caine is a singer-songwriter who previously resided in Nashville and has recently returned to town.
Introduced in the episode (Now and Then There's) A Fool Such as I, she is a former Nashville native who has recently returned to town after some time away. She performs at an open mic night at The Bluebird Cafe and afterwards talks to Deacon about Rayna.
In the episode Ghost in This House, she meets Zach Welles at the Highway 65 offices and is interested in signing with the label. Zach has a word with Deacon, telling him that she was previously married to label boss Brad Maitland, and when she meets up with Deacon they talk about previous relationships but when he phones her after she contacts him about her showcase she believes he is romantically interested in her but does not feel the same way and hangs up on him. He later shows up at her showcase but leaves when her song hits an emotional cord with him.
She attends at charity fundraiser in the episode The Night Before (Life Goes On) and switches Deacon's name card to another seat as she does not want to sit next to him. However, when her ex-husband arrives and starts commenting about their son, Deacon sees how uncomfortable she is. They encounter each other outside and she starts talking about her son and how Brad tried to turn him against her.
In the following episode, Deacon tells her that Scarlett had a miscarriage and Jessie decides to leave over some items to Scarlett's house before the latter invites her in for coffee. Jessie reveals that she had several miscarriages over the years so she knows what Scarlett is going through. Deacon later introduces her to Maddie and Daphne.
She does not have an easy time with her ex-husband being in town since he is making life hard for her, saying she is in breach of the court order in regards to their son. When Deacon faces trouble with Highway 65, she brings him to the lake so that he can take time to figure out things for himself. After performing at the Opry, Daphne sees them hug and begins to worry that Deacon may be moving on too fast but Deacon reassures her that she and Maddie are the two most important women in his life.
Over the next few months, her friendship with Deacon has grown into a romantic relationship, although she reassures him that she is not trying to replace Rayna. Maddie is unhappy about the relationship and makes her feeling known by being rude to Jessie until the two have a heart-to-heart, which leads to them starting to get along better.
Jake eventually reveals to his mother that his father intends on sending him away to boarding school and refuses to leave his room or talk to her. When his father shows up, a fight breaks out which is broken up by Deacon as a shocked Jessie looks on.
Brad issues Jessie with a court summons demanding full custody of Jake. Due to the pressure, Deacon and she decide to split up. She tells Alannah to be careful of Brad and after the latter notices his womanising ways she decides to teach him a lesson by getting not only Zach and Deacon involved but also Jessie and the other women he has harassed. Jessie demands full custody of their son, which he grants.