sed 's:^Comment=\(.*$\):Comment='\''<span size="xx-large">\1</b>'\': \ $HOME/3dchess.sh
Add -i when you are sure you have what you want.
Breakdown:
s:x:y: - This is the overall replacement pattern, basically replace x with y. Obviously we have a lot more between the colons above! Usually : is / but sed takes whatever comes after the s and using / here would mean you need to escape it in the pattern.
^Comment= - regex match Comment= at the start of a line ( ^ ). Good practice since it is possible (though unlikely) to get this elsewhere, which would cause problems.
\(.*$\) - match anything ( .* ) up to the end of the line ( $ ). Surrounding with \( \) creates a back reference for use later.
'\'' - close the '' quotes, put a literal ' and reopen quotes. Alternative method to @terdon's.
Comment=<span size="xx-large">\1</b> - replacement string, \1 is the backreference from before.
'\': - close quotes, put a literal ' then the final colon.