It's easy to get to Puebla from DF on the luxury buses operated by Estrella Roja/ADO, which leave both terminals nearly every 30-60 minutes and cost about 200 pesos one-way. You can go to the CAPU station or 4 Poniente stations (the latter is closer to the historic center).

There's so much to see, do, eat and explore in and around the Puebla area that it would be tough to recommend an itinerary without knowing your specific interests. For some pointers, check out my blog, AllAboutPuebla.com. Enjoy your trip!

A week is pretty long for Puebla. And I love the place, but usually sepnd only 3-4 days there.

Spend one full day doing a self-guided walking tour of al the churches, the calle de dulces, etc. End up at the outdoor reafts market and outdoor artists market area.

Go to Cholula (30 min. by colectivo from Puebla centro) and see the pyramid there- although it is unexcavated it is the 2nd largest in the world, and tunnels underneath the pyramid can be gone through, which is pretty cool. Also the active volcano is a few miles right behind the pyramid, so if you hike up to the top of the pyrmid where a church has been built, you can see the volcano on a clear day. Try to go to Cholula on market day.

Try to spend a leisurely Sunday in Puebla. Many markets are set up in the parks around the centro, including a very good antique market and a nice family style market w/live music. Lots of good street food also on Sundays. It is my favorite day in Puebla.

It is also possible to visit Tlaxcala from Puebla. Another lovely colonial town, and if you want to see a bullfight, they sometimes have them in the wonderful ring there, right in the city center. Tlaxcala is the area where all the bulls are raised.
I did a day trip to Atlixco from Puebla on my last trip. I to recommend it, found nothing of interest there reall, except that on the way there there is an Italian village where lots of Italians have made home and there are some GOOD italian restaurants there.