I just went through this process, so here's what I've learnt:

• VFS has an office in Pune, so you can apply in person in Pune, without having to go to Bombay.
• The VFS website will help you figure out which form you have to fill and which documents to carry. Download/print the form.
• You can use the online appointment scheduler to get an appointment for submitting your application to the VFS office. Right now, there appears to be a 12 day waiting period (i.e. if you apply today, you'll get an appointment for 12 days later).
• However, you don't have to take an appointment. Walk-ins are also allowed - on a first-come-first-served basis. If you do walk-in, try to reach the VFS office by 7am. If you do that there's a chance that you'll be done by 9:30 or 10. If you reach by 7:30, you'll probably be done by 12-noon. Reaching later than 8:30 is not recommended.
• Make sure that you don't have Mehendi or anything else on your hands. They can't take your fingerprints in that case, and you will not be able to apply
• You can pay in cash, so don't bother with a demand-draft...
• Security will not let you take anything inside (e.g. bottles of water, etc), so try not to take anything other than your documents. There's no place to keep your stuff outside.
• Eat something before you go. There's nothing to eat there, and you might be stuck there for 5+ hours without food.
• The VFS office is right next to Bishop's School, just off of Nagar road.