Traveling to Slovenia via Eurail?

I’ll be traveling to Slovenia from Florence and then from Slovenia to Romania this summer via train. Given that I’ll be arriving in Ljubljana and departing from there, I am wondering if it makes the most sense to find lodging there. However, I am conflicted because I feel I would be missing out on so much if I didn’t stay somewhere more picturesque. If you had 5 days in Slovenia, where would you stay to capitalize on what Slovenia has to offer without sacrificing logistics?