Yeah, that is a pretty slow pace for Slovenia, but that's OK if that's what you prefer.
Make sure to buy a vignette driving sticker at the Slovenian border! You need one to drive on the highways, or you risk a steep fine, with no warnings for naive tourists.
Ljubljana is really small (though it's wonderful). Five nights there is a lot if you will have five nights up at Lake Bled also. I'd have some day trips lined up for sure. It's a great place to come back to at night.
Driving between Ljubljana and Bled, be sure to drive via Skofja Loka and then take the mountain route via Jamnik and Kropa and down to Bled - very scenic and beautiful, and with the time you have, you can spend the whole day doing this if you want. Skofja Loka is wonderful and worth a few hours. There are lots of little stops along the way (the route is quite narrow, so try not to rent a big car even with five people!).
Bled is touristy, a built-up tourist resort. It's a very convenient base for the area, not a mistake to stay there, but if you want a more back-to-nature experience, consider nearby Lake Bohinj instead (much less built up) or the little town of Radovljica (more of a "charming old town", but very small).
Piran is lovely too. Four nights there in the summer would make more sense but in May it may not quite be warm enough to swim. Again, plan a lot of day trips - know what you want to do in the area. I think some people might prefer going south to Croatian Istria, to see the hill towns there, perhaps the Roman ruins down in Pula. You can certainly day trip there from Piran, but then you have to keep crossing the border. Rovinj is somewhat similar to Piran, another lovely old fishing village (now also quite touristy) and makes a good base for this area. Make sire your Italian rental car lets you drive into Croatia.
For another base in Slovenia, consider Maribor in the east - a different look at country vs. the much-more touristed western part. Nearby Ptuj is the oldest town in Slovenia I think. You can also day trip out there from Ljubljana.