For anybody interested, I've done a lot of research on the "collectible" versions of all of the books in the Ender and Shadow saga. I've put all of the editions I know of below. I welcome corrections and additions! As far as I can tell, there's not one place on the internet where this information is gathered.
Ender's Game
Easton Press Leatherbound Signed Edition
Tor Books Leatherbound Signed Limited Edition (Limitation Number Unknown)
Easton Press never released the number of copies sold; I suspect it is a few hundred. I've never seen a copy of the Tor edition to find the limitation number.
The first edition of Ender's Game is also highly collectible, especially if signed. Signed copies of the 2006 gift edition are also prized.
Speaker for the Dead
Easton Press Leatherbound Edition (Limitation Number Unknown)
Easton Press never released the number of copies sold; I suspect it is a few hundred. It seems to be rarer than the Ender's Game Easton Press edition, and it is unsigned. I'm not aware of a signed limited edition.
The first edition of Speaker for the Dead is also highly collectible, especially if signed.
Xenocide
Tor Books Signed Limited Leatherbound Edition - Limited to 325 Copies, 300 Numbered, 25 Lettered
Children of the Mind
Tor Books Signed Limited Leatherbound Edition - Limited 100 Copies, 75 Numbered, 25 Lettered
Ender's Shadow
Tor Books Leatherbound Signed Limited Edition (Limitation Number Unknown)
I've never seen a copy of the Tor edition to find the limitation number.
Shadow of the Hegemon
Tor Books Leatherbound Signed Limited Edition - Limited to 125 Copies, 100 Numbered, 25 Lettered
Shadow Puppets
Tor Books Leatherbound Signed Limited Edition - Limited to 125 Copies, 100 Numbered, 25 Lettered
Shadow of the Giant
Tor Books Leatherbound Signed Limited Edition - Limited to 100 Copies
I believe all are numbered. I've never seen a lettered version.
Ender in Exile
Tor Books Leatherbound Signed Limited Edition - Limited to 100 Copies, 75 Numbered, 25 Lettered
First Meetings
Subterreanean Press Signed Limited Edition in Slipcase - Limited to 350 Copies
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This is different than the mass market version, which came out later and includes an extra story.
The version sold at EnderCon - which is still a SubPress version, but without the limitation page and signature - is the true first edition.
Other Collectibles
August 1977 Edition of Analog Magazine - Includes the Original Version of Ender's Game
Easton Press Maps in a Mirror - Signed First Edition - Includes the Original Version of Ender's Game
Ender's War - Book Club Book - Contains Both Ender's Game and Speaker for the Dead Together
Advance Reader Copies and Proofs
I've seen advance reader copies (ARCs) or proofs for the following books: Ender's Game (rare), Speaker for the Dead (rare), Xenocide (common), Ender's Shadow (common), Shadow of the Hegemon (common), Shadow Puppets (common), First Meetings (common).