If you have a set of gages ($59.00 at Harbor Freight) you can easily purge the system with no fear of getting frostbite. You connect the high and low couplings to the high and low ports of the A/C plumbing and you open up the shut off valves just under the gage. While the system is draining you will see frost build on the lines and it will be extremely cold so do not touch. After this is done you can then replace the Schrader valve. If you have an old Freon can connector in your possession (obviously you do since you refill yourself) all you have to do is connect the quick connect coupling to the A/C port (with the shut off valve close of course) and then slowly back off the valve to let the Freon escape. This will allow you to evacuate the system with no fear of frostbite. However, you want to avoid breathing the gases. The Freon has oil mixed in and the oil vaporizes when you open the system to atmosphere. This gas/oil vapor is carcinogenic. Where a mask while opening the valve and then walk away. After everything leaks down you can then replace the valve.
However, there is one major problem. Before you can refill the system with R134a you haven to pull a vacuum on the system to remove any moisture that may have gotten in while you had the valve removed. A cheap vacuum pump capable of puling a good enough vacuum for an A/C system will cost you no less than $100.00. Most are $150.00+. Then you have about $50.00+ of R134A you have to buy to refill the system! You will easily exceed $200.00 to do this the first time. You will most likely exceed $250.00 and it's possible to exceed $300.00. You can do it for under $200.00 if you order everything ahead of time from discount suppliers (from china) and wait 30+ days for everything to arrive.
There is one more option and I have not even tried this yet. For $100.00 there is a tool on AMAZON.COM that claims to allow you to change a Schrader valve with NO FREON LOSS!! http://www.amazon.com/Loss-R134a-Valve-Remover-Installer/dp/B011T6LUI4/ref=sr_1_29?s=automotive&ie=UTF8&qid=1437171136&sr=1-29&keywords=R-134a+Service+Port+Adapter
I've already hinted to the wife that I NEED this tool! Merry Christmas! It comes with adapters for the low and high pressure ports. I have no clue how it works. It sounds pretty sketchy, but if it works it will change life forever for the DIY types! I had a leaking valve on my Dakota R/T for 4 years and I just kept throwing money away on more Freon. I finally broke down and bought enough Freon to do the job and changed the whole valve out. I was out nearly $100.00 for the new valve and all new Freon. Had I known about this little device I would already have purchased it.
Of course, you could just take it to a shop with the APROPRIATE HVAC equipment. They will have a Freon recovery system that will capture all of your existing Freon and then put it back in when they are finished servicing the system. The typical cost for such a service is under $200.00. So if this is a 1 time deal you would save money by paying a professional to do this. If you have 4 cars like I do and you do all your own work then it may be a good investment to buy a set of gages and a vacuum pump.
Also, R134a is supposed to be environmentally friendly (does not deplete ozone). That is why you can buy it without a license. In other words, the EPA, CIA, and the FBI won't be showing up at your door if you leak this stuff to atmosphere. If you had an older car with R12 it would be totally different! I think all cars made after 1994 have ozone friendly R134a Freon.