At the enterprise level you have varying options. At my current employer the path looks like this...
- Sr. Programmer
- Lead Programmer
- Lead Technical Architect
- Director (Technical)
There are Directors at both the Technical side and Business side. One manages technology and the other manages people. The VP tier is essentially where they converge.
In addition we have a .NET Architecture Team and a Java Architecture Team responsible for their given technology across the enterprise. Heading into one of those teams will allow you to narrow your focus and become more of an expert in a given area. You could argue that this could be defined as Enterprise Architecture as mentioned in your question.
Once you reach Director (Technical) you essentially move horizontally across business units; unless you want to begin having a larger focus on managing both people and technology along with providing value to the business then you begin to move up the corporate ladder starting at the VP position.
CIO/CTO is a different beast in and of itself within an enterprise all together.