You cannot block all possible workarounds to access a certain webserver but you may use a layered approach to make it very hard for the average end user to access said blocked content
- Allow/Block traffic based on destination port(e.g. only allow tcp/80, tcp/443, udp/53)
- Allow/Block traffic based on destination URL (e.g. block category PORN, Web-Proxy)
- Allow/Block traffic based on application (e.g. only permit http,https,dns)
A policy as stated above may be implemented by using a modern firewall that is capable of L7 firewalling (e.g. Cisco FirePower, Palo Alto Networks, Checkpoint, Sophos, etc. etc.)
I have only listed a few vendors for reference. There are many solutions for your problem and a firewall capable of deep packet inspection may be the best fit to solve your issue.