Originally Posted by Danny Stewart
The Beginning Boxset
(An Unearthly Child, The Daleks, The Edge of Destruction)
The Tomb of the Cybermen
Spearhead From Space
Genesis of the Daleks
The Talons of Weng-Chiang
New Beginnings Boxset
(The Keeper of Traken, Logopolis, Castrovalva)
The Five Doctors
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As far as "firsts" go, I'd say definitely Tomb, Spearhead, Genesis, The Beginning and New Beginnings. However I think Five Doctors is a bit too convoluted and Talons while being good is a bit unorthodox for a Who episode.
I know Kody is familiar with the series so all those should be fine but for first stories in general...