Changing mail address in steam

I have been using Steam for a few years with over a 100 games on my account.. Due to recent Issues i needed to change my email address which i successfully achieved for my bank,paypal,ebay etc with no problem I have hit a brick wall with steam.
I follow the instructions and fill in relevant info, and receive a 5 digit captcha but when entered steam says it doesn't recognize it and I have to start all over again. I Have tried this 3 times without success and on the 2nd & 3rd attempt had a witness to make sure I had entered correct captcha correctly.
What do I do now, There is no other way of contacting them?
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