First and most obvious, when analysing business processes and designing technical solutions, involve and listen to key users of affected systems. Some technologists still fall into the trap of masterminding broad organisational change behind closed doors. Being a chief technology officer (CTO) does require quite a bit of "out of the box" thinking, but outcomes are always better when on-the-ground realities inform that thinking.
The best way to get started on these projects is to walk around, observe what people do and ask questions. Of course, you also need formal meetings and fact-finding projects to understand how and why current processes are the way they are. Quite often, these efforts uncover explanations of the way processes are supposed to work, rather than how they actually work.
As the layers of the process onion peel back, you may learn that your initial process improvement ideas make little practical sense. But having your assumptions proven wrong up front is a lot less expensive than trying to jam the wrong system into your organisation because you didn't adequately consult the users.
If you reach an impasse, do some external networking. Understanding how similar businesses handle process change is invaluable. Fortunately for CTOs in some cities, a number of local clubs are growing for that very purpose. New online services like LinkedIn make it relatively simple to contact colleagues in similar roles at similar companies. Although it might not be possible to talk directly to CTOs at your closest competitors, CTOs at companies within your general industry are often willing to share information. For me, that means regular conversations with CTOs at consumer media companies and B2B publishers outside of my publication's competitive landscape.
Keep in mind that input from industry colleagues and business stakeholders only gets you so far. A good CTO should also lead and be prepared to take informed risks that go against the grain. A new system or platform shouldn't drive change, but it may provide the force necessary to break organisational inertia. Don't waste the opportunity when it comes along.
In most environments people are reluctant to change the way they do things and frequently try to incorporate the inefficiencies of a legacy system into a new one. When they succeed, bad processes become even more deeply entrenched. Because you'll have to deal with the consequences, it may be worth spending some political capital to hold the line against duplication of absurdity.
That said, CTOs should use the power of persuasion judiciously as they fight the good fight. Be respectful of those who know how things ultimately need to work. There is a fine line between aggressively moving your organisation forward and giving IT a bad name. Walking this line has far more to do with how well you exercise your people skills than the depth of your technology expertise.