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That day, I had been working in London and I was on my way home when....

or

That day, I had worked in London and I was on my way home when...

(I am on my way home after the working day)

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Depends what you want to say

(On) that day, I had been working in London and I was on my way home when....

Has a feeling that you normally don't go to London, but happened to be in London working.

(On) that day, I had worked in London and I was on my way home when...

Has a feeling that you work in London from time to time, and worked in London that day.

(On) that day, I worked in London and I was on my way home when...

Has a feeling that you habitually work in London.

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