What is the name of the poem written by Charles, Duke of Orleans as
the first Valentine -- to his wife while he was inprisoned in The
Towers of London  - where can I get a copy? web site?

I haven't been able to find a copy of the original French poem, but
this English translation of one of Charles's poems may be of interest:

http://www.worldwideschool.org/library/books/youth/holidaystories/goodstoriesforholidays/GoodStoriesforHolidays-Valentine/chap1.html

Some of Charles's poems, in French, may be found here:

http://www.bartleby.com/244/20.html
http://www.bartleby.com/244/21.html
http://www.bartleby.com/244/22.html
http://www.bartleby.com/244/23.html
http://www.bartleby.com/244/24.html
http://www.bartleby.com/244/25.html
http://www.bartleby.com/244/26.html

This web site claims the poem is at the British Museum's manuscript collection:

"Then there was a love letter, complete with poetry, written by the
French Duke of Orleans,
Charles, to his wife. This letter was written while incarcerated in
the Tower of London. He was
captured at the Battle of Agincourt, in 1415, and probably thought he
was to be executed at any
moment. He actually stayed in the Tower for 25 years and died a free
man in 1465. This letter,
along with much of the duc d'Orleans' poetic works, can be found in
the British Museum's
manuscript collection. None of his work could really be called a
Valentine poem so this can be
debated as the first valentine as well."

http://www.i-love-my-wife.com/guest-articles/first-valentine.htm