The entertainment card comes with the purchase of the Entertainment Book sold in many cities. I believe the url to purchase one onsite is entertainment.com. You can book your hotel before purchasing the Entertainment Book, but must have the card with you when you check in. The current book expires in November, so keep that in mind if your trip is after that date. Just wait to get the new book. If this book is offered in your city, you do not have to purchase the Orlando book for the hotel discount.
The Loews First program will not land you a discount on a hotel room but will get you an upgrade when available. I just came back yesterday from the HRH. I booked a pool view room at $129ish/night and was upgraded to their Club Level at no charge. I sent a fax about five days before our trip requesting the complimentary upgrade. Guests on the Club Level enjoy a complimentary continental breakfast (bagels, donuts, croissants, yogurt, fruit, cereal, coffee, tea, juice) every morning. From 5:00pm -7:00pm complimentary cheese, crackers, raw vegetables/dip, wine, beer and soda is served. And....8:30pm-9:30pm....milk and freshly baked cookies are served. Aside from this, service on this level is outstanding.