maddocks,
The key is where the valve is located in the piping. The piping from boiler shell to first valve (second valve in blowoff piping) is in the jurisdiction of ASME B31.1 as "Boiler External Piping" or BEP. This piping has practically all the same type of documentation and AI stamp as the Section I Boiler requirements. Piping that is beyond that valve could be B31.1 Power Piping Code, but as "Non-Boiler External Piping" or NBEP, with less exam and documentation, no AI stamp. The piping beyond the valve could also be in jurisdiction of B31.3 Process Piping Code, if the Owner so chooses, as metengr has pointed out in the B31.3 diagram to illustrate.
Another way to look at the break point is to consider the extents of a boiler hydrotest. The annual boiler inspection will include a hydrotest. The piping with valves that will block in the boiler will be within B31.1 Power Piping BEP. If the boiler is in a power plant, most likely the Owner will have all the piping in the power plant designed and built to the B31.1 Code, NBEP. A process or chemical plant owner would be likely choose B31.3 process piping Code that has different design, test, and construction. You need to have Owner state what Code that is his choice for the piping beyond the boiler valves. Be careful since "Boiler External Piping" has different meaning to Authorized Inspector, than to say the piping external to system.
The B31.3 exam and test requirements will have more radiography exam than for B31.1 at moderate psi design. The pipe wall thickness of B31.1 will likely be thicker due to lower design allowable atresses of Power Piping Code.