When I started my Thoth journey many years ago, I had solid astrological knowledge but until recently, I knew little about kabbalah (I know Hebrew, though, and that certainly helped). I found Zephyros and others here on AT a great source of knowledge and wisdom.
I think it's possible to read the Thoth intuitively, the images are strong enough. Write everything down; at a later stage, you may discover depths in your readings that you don't see now. Don't transfer the RWS meanings to the Thoth, though, that would do both a disservice. Read the images, use your books, and try to acquire the knowledge while you work with the deck. It's better IMO to absorb knowledge while doing your readings that interest and concern you, than reading a dozen books and then trying to coordinate and integrate it all.
I'd really do both, read your cards and read your books.
I drew a study Tree of Life and pinned it to my wall, and that helped. A study zodiac and diagram of the planets might help, too. There are many good lists and diagrams you might wish to print out. Color-code them with the elements, that helps for astrology.
I didn't tackle alchemy yet. Read some books but somehow, the knowledge doesn't "gel" with me, I didn't yet find the key. It was a happy moment when for the first time after reading so much about it, the Tree of Life and other kabbalistic concepts made sense, real sense.
Enjoy your journey!