Good question. For me, they are similar but used a bit differently nowadays at least. I would like to offer my understanding.
天真 has a positive connotation if used to describe a child which focus on 真 true to yourself (e.g. 孩子天真的笑脸), however used on adult implies naive in a negative way. For example we say someone has 天真的想法/做法 which implies this person is unrealistic and not mature. But when we describe someone with 单纯, we focus on 纯 pure in nature. We talk about someone 单纯 is normally positive means someone simple and pure. It's not simple minded but also has a hint of cleanness in it. We can look into the two characters separately for your understanding: 1. 单, 简单, 单身, 单人床 all says single 2. 纯, 纯洁,纯净,纯粹 all about purity. Beside talking about someone 单纯, we can also say 单纯的生活
Hope this helps. I am just a native speaker not a teacher. :)