A simple file comparison can easily be done using some checksumming (like MD5) or just reading both files.
However, as Excel files contain loads of metadata, the files will probably never be identical byte-for-byte, as James Burgess pointed out.
So you'll need another kind of comparison for your test.
I'd recommend somehow generating a "canonical" form from the Excel file, i.e. reading the generated Excel file and converting it to a simpler format (CSV or something similar), which will only retain the information you want to check. Then you can use the "canonical form" to compare with your expected result (also in canonical form, of course).
Apache POI might be useful for reading the file.
BTW: Reading a whole file to check its correctnes would generally not be considere a Unit test. That's an integration test...