XML uses Unicode, not ASCII.
You can't get the Unicode code for a character in XSLT 1.0. In 2.0 you can use the functions string-to-codepoints() and codepoints-to-string(). Alternatively your needs may be met by <xsl:number value="position()" format="A"/>.
Michael Kay
http://www.saxonica.com/
Author, XSLT Programmer's Reference and XPath 2.0 Programmer's Reference