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First of all, if a key contains more than one item (aka it's a bundle/package), then it WILL activate regardless. Stuff that you already own will simply be discarded, you only get the stuff that you don't have.
Every once in a while, there are also claims that Steam will silently discard a key if it's just a slightly different version of something you already have.
Just keep in mind that Steam only cares about money. if you loose a key without getting anything, or not all of it, they are happy. So be careful.
Are the two items in the page highlighted with the blue "IN LIBRARY" tag? If so then you already have everything.
If this key is for the BUNDLE of games plus DLC, you're stuck.
1. Rome: Total War™ - Collection (id: 4760)
2. Rome: Total War™ Collection (id: 463)
Although only the 463 package containing everything is available for purchase currently, at one time the 4760 collection as well as the stand-alone Alexander expansion were available. It would have been very easy to have mistakenly purchased the 4760 package and assumed that it had the Alexander expansion. If so then you will need to purchase the full 463 package. Otherwise, I would contact Steam and see if they can rectify the situation.