「When doing ~, take advantage of that time to also do ... .」 Used when you want to say you accomplish two separate things at the same time. ~ is the primary action; ... is an additional, purposeful volitional action.
例:
1. 散歩のついでにこのはがきをポストに出してきて。
While you're out for a walk, drop this postcard in the mailbox.
2. 玄関の掃除をするついでに靴の整理をしよう。While we're cleaning the entryway, let's organize the shoes too.
3. インターネットで本を注文したついでに新しく出たDVDも調べた。I ordered a book online and, while I was at it, looked up the newly released DVDs.