In Sigil if you right-click on the styles folder on the book browser, you will have an option to add an existing file.
So if you have already got a created CSS file (I have one with all my standard CSS content in it so I can delete what I don't need after the epub is ready), you choose this option and navigate to where the file is and select it.
Now it will be loaded into you epub, you only will need to link it in (needs to be done manually at the moment).
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