For most practical serialization needs Protobuf is good enough and it is conceptually simpler.
I don't have plans for supporting capnproto at the moment. However there shouldn't be a problem with mapping capnproto definitions to Piqi and adding support for capnproto format. Piqi is extensible enough and should be able to accommodate that. It could be a fun project. Why not?
If somebody is willing to play with this idea, I'd suggest to start by adding capnproto as one of the serialization formats for 'piqi convert' and multi-format serialization (along with XML and JSON). Plus, of course you need to implement converters between .piqi and .capnp schema languages.