Up front, let me say that my response will be colored by the fact that I was in running for a CTO position of a fairly large company. I do not have any government background also.
CTO jobs generally mean different things in different companies. In situations where there is a CIO and CTO, generally CTO works within guidelines and strategies visualized by CIO and other C-level executives. CTO is concerned primarily with operational parameters like capacity building, capability building, and even confidence building.
CTO generally understands current technology trends, has an antenna up for receiving tectonic technology shifts, and can visualize alignment of company's business goals and technology goals.
Somebody from Silicon Valley will have feelers for technology shifts that may be difficult to replicate elsewhere. Aneesh Chopra, from limited background given in submitted story, may excel at alignment, particularly in a government position with multitude of stake holders. He seems quite capable of understanding current technology trends as any person from Silicon Valley.
So the question basically boils down to this - if CTO of USA is mainly responsible for operational issues as defined above, he is an excellent choice. On other hand, if CTO of USA is charged with coming up technology that nobody can even visualize now, there may be better choices.