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I think its going to be pretty hard to find a decent starting position that allows you to work from home, especially without relevant work experience. I'm in the US, so I am not really familiar with the general attitude of businesses in the UK when it comes to telecommuting. Still, I think it would probably be easier to establish yourself with a company that embraces telecommuting/remote workers, then explore the option. You can also explore being an independent subcontractor, but that can be very uneven work.
Working from home can be quite challenging, in my experience. It can be very easy to have a nice long cup of coffee and then have another, then take a break, then have lunch, then watch the news, then play with the cat, then realize it is 4 p.m. and you have gotten exactly nothing done. As much as I liked the freedom, I found that I was not well suited to an unstructured work environment. I suggest that you honestly assess whether it would be a good fit for you before putting too much effort into it. Good luck if you do seriously pursue it!