Hi there...
The two editions are identical except for capacity. Both offer the same replication and SLA.
Web Edition scales from 1GB to 5GB, whereas Business Edition scales from 10GB to 50GB in 10GB increments. The only thing you'd need to worry about, if you had an MSDN Premium or BizSpark account, is that you get 3 free 1GB Web Edition databases. If you add a Business Edition database, you'll incur costs.
Both allow you to set maximum size on the billing boundaries (1 or 5 for web, 10, 20, 30, 40, 50 for business). And both are billed on an amortized schedule, where your capacity is evaluated daily, and your daily rate is based on which tier your capacity falls into.
Regardless of edition, you have the exact same set of features - it's all about capacity limits. You can easily change maximum capacity, or even change edition, with T-SQL. For instance, you might start with a Web edition:
CREATE DATABASE Test (EDITION=’WEB’, MAXSIZE=1GB)
Your needs grow, so you bump up to 5GB:
ALTER DATABASE Test MODIFY (EDITION=’WEB’, MAXSIZE=5GB)
Now you need even more capacity, so you need to switch to one of the Business Edition tiers:
ALTER DATABASE Test MODIFY (EDITION=’BUSINESS’, MAXSIZE=10GB)
If you ever need to reduce your database size, that works just fine as well - just alter right back to Web edition:
ALTER DATABASE Test MODIFY (EDITION=’WEB’, MAXSIZE=5GB)