I'm not sure if XCC Mixer works with the BFME big files without modification, the version I have doesn't.
I use a hex editor first to open the big file then change the forth byte from a 4 to an F. This will allow you to open the BIG file with either FinalBig or XCC Mixer.
Then do your mods, extractions whatever and remember to change the F back to a 4 later.
Search google for Hex Editor, its available as a free download, make sure you do this on a copy of the BIG file not the original, just to be safe.
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