Samsung Smart TVs will most likely not let you install Xibo player on it, besides they do not use Android (or Windows) OS either, in most cases they use Samsung specific OS (or pre configured Samsung digital signage software). Even if they do run on Android, you will most likely not be able to install Xibo for Android on it as Xibo is not in the play store.
There could be ways around it, but that's against Samsung ToS and is therefore not recommended.
As you said, you can use it as a TV connected to an android box (or windows PC) with Xibo client installed on it.
If you're interested in android devices, please have a look at our recommended android hardware list.