The EBS Snapshots will give you a slightly different type of backup than then WAL-E backups. EBS backups the entire drives, which means if your EC2 Virt goes down you can just restart the virt with your last EBS snapshot and things will pickup right where you last snapshotted things.
The frequency of your EBS snapshots would define how good your database backups are.
The appealing thing about WAL-E is the "continuous archiving". If I needed every DB transaction backed up, then WAL-E seems the right choice. Manys apps I can envision cannot afford to lose transactions, so that seems a very prudent choice.
I think your plan to snapshot the production volumes as a baseline, then use WAL-E to continuously archive the database seems very reasonable. Personally I would likely add a periodic snapshot (once a day?) to that plan just to take a hard baseline and make your recovery process a bit easier.
The usual caveat of "Test your recovery plans!" applies here. You're mixing a number of technologies (EC2, EBS, Postgres, Snapshots, S3, WAL-E) so making sure you can actually recover - rather than just back - is of critical importance.