the larger and more insature is the molecule the more stable is the radical (you spread a charge on a wider space polar groups that attract electron in connected may help)
Everything is about ratio. So if you are expecting a descent yield of N-radicals, you can still use DMPO. You'll be able to easily distinguish between N- & C-centered radicals using EPR. Importantly, you need to make sure that during processing your samples you do not introduce cosubstrates which could be co-oxidized and give rise to secondary radicals from the anticipated N-radicals.