I'm not sure you can as Hotmail is a web based mailing system. Unlike Outlook and Outlook express which are dedicated mailing systems.
With these two you can switch between the two as they are directly connected to your ISP's server via the long details supplied by them.
I use BT's webmail service as I was signed up to them before I moved as you can check your mail from anywhere in the world. Unlike dedicated programs Outlook/Express for example which would need to be installed on the PC.