The card art is located in DATA_DECKS_D14.WAD. In the Wad they are located in DATA_ALL_PLATFORMS\ART_ASSETS\ILLUSTRATIONS and are named according to what is listed in the individual card XMLs in the ARTID tag.
For example
Aegis Angel has:
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<ARTID value="131605" />
So you would look for 131605.TDX in the ILLUSTRATIONS directory.
Yes, it is possible to change the art. The best method would be to simply make a new mod with the ILLUSTRATIONS directory in it and simply include a new image for the card (named exactly the same) and it should override that in the base game wad (this way you don't change the card XML at all so if there is a bug another mod like my Core Fixes can fix the card without interfering with your changed image and your image changes won't interfere with mods that change the base cards like my Core Fixes).
If you don't want to unpack the DATA_DECKS_D14 wad to get at the ARTIDs you can load up my Deck Builder and right-click on the card and select "View Card" from the context menu and you can see the card's code (including the ARTID tag).