There are three walks that start from Podere Sant'Angelo without having to use your car:
There are several signed trails that start from Roccalbegna. A challenging, but rewarding, full day's walk is to take the trail that leads up to Monte Labro. This starts just outside the village and is well signposted. It's uphill all the way! There are a couple of shorter walks around the village and along the Albegna river.
Duration Roccalbegna <-> Monte Labbro: 5 hours Difficulty: moderate (all uphill to Monte Labro)
You can also walk around Monte Labro from the Parco Faunistico near Arcidosso. To do this park up by the entrance to the park and follow the trail on the map you'll get with your entry fee.
Duration: 3 hours Difficulty: moderate (some steep sections)
This is an interesting day's walk through the Etruscan landscape of the very south of Tuscany. The route takes you along part of a 'via cave' (a road cut out of the soft pumice rock by the Etruscans) and then along trails that take you past Etruscan remains and there are also some sections along roads (with next to no traffic). There are several 'trattorie' and a couple of bars in Sovana, before heading back to Pitigliano visit the 13th century cathedral.
Duration: 5 hours Difficulty: moderate (some short, steep sections along the 'vie cave')
The tiny village of Bagni Vignoni is famous for its hot springs and the large pool at its centre. Its location on the slopes of the Val d'Orcia makes it a great location for lots of great views over this iconic Tuscan landscape. There's an interesting circular three hour walk that takes you down to the river Orcia then back up to the hills above Bagni Vignoni from where you can look over to Pienza and Montalcino, you then return to Bagni Vignoni passing through the small hamlet of Vignoni.
Duration: 4 hours Difficulty: moderate (some steep sections along old mule tracks)
This walk starts from the car park of La Foce manor house. The house and its beautiful garden are worth visiting before setting out on this well signposted walk around the southern edge of the Val d'Orcia. For the first half of the walk you pass through oak woods before arriving at the hamlet of Castiglioncello del Trinoro with its five star 'albergo diffuso' (hotel with rooms spread throughout the hamlet). There are spectacular views across the valley. You walk down 'strade bianche', then along the side of the valley back to la Foce with amazing views across to Monte Amiata along the way. Finish the day off with a snack or dinner at La Foce's great trattoria, Dopolavoro.
Duration: 4 hours Difficulty: moderate (there are a couple of steep sections)
Ask your host for more information about any of these walks.