The National Currency Collection has a vast amount of material, only a portion of which has been catalogued online. I'm quite confident that the above-mentioned Edward VIII item is in the collection, but good luck finding it online. A lot of the more "interesting" material such as trials, proofs, etc, particularly of material that never made it to circulation, or that is relatively new will not likely be on the website.
You can always send the Museum an email asking about it.
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BWJM, F.O.N.A.
Life Member of CPMS, RCNA, ONA, ANA, IBNS, WCS.
President, IBNS Ontario Chapter.
Treasurer, Waterloo Coin Society.
Show Chair, Cambridge Coin Show.
Fellow of the Ontario Numismatic Association.