Maaloula is one of the few cities in the world where they still speak the western dialect of Aramaic, and according to the monastery on the top of the hill this was the language Jesus had spoken.
Nevertheless, if you're not interested in those religious things, it's worth to visit Maaloula, it's beautiful canyon and the view down from the hill. Additionally, you can get some free wine in the chapel museum, just sit down on the couch inside the museum and wait some minutes until the saleswoman serves you.
The main highway is just 12km away from Maaloula. From the city center - which in fact is the roundabout in town where all minibuses stop - walk up the road away from the hill. Have a look on the picture, the road out of town is the road on the right side. Hitchhiking is possible everywhere along this way, just take a walking distance from the minibuses, as they will try to catch you without any fear. Follow the road for 12 km.
Another option for going south towards Damascus is via Saidnaya. There's very few traffic between Maaloula and Saidnaya, only some trucks stopping half way for filling up with sand or minibuses. Nevertheless it's possible and easy to hitchhike, of course. For going this direction, take the same road than described above, but after 1-2 km out of town, the road splits. For going via Saidnaya, take the right fork.