Modifing Cisco access list

in my access list i have a line that says (near the top)

access-list 111 permit tcp any host 1.2.3.4 eq smtp

now i've written a script that goes through mail log and looks for ip's that are blocked by spamcop and want to block these from sending any future emails but it's not working

i'm adding this to my access-list

access-list 111 deny tcp host 121.147.116.226 any eq smtp

my question is since this is below the line allowing everything is that why it's allowing the mail to continue to come in?

if so is there any way to do this easily? i'm using perl and net::telnet to automatically (every hour or so) telnet to the cisco box and add these lines .. how do i force it as a rule ABOVE the permit line?