Andy,
From what I have read, I am not sure if composite keys have made it into the main branch of PetaPoco, or for that matter, the version of PP used DNN's DAL2.
But if it is there, you would do it like this:
[PrimaryKey("field1,field2")]
If that doesn't work, then it is not supported yet. You may have to change the table schema to use an identity as the Primary Key and the make the composite key a unique constraint. You can still query the unique constraint using the Find().