The good thing about Milan is that most of the things to see are very close to each other, all in an area of around 1km from the centre of Milan.
1) Starting from the centre the first thing to visit is the famous Duomo, the 4th largest cathedral in europe. It's a big thing and really impressive, with its gothic architecture. You can also climb on top of it and have a great sight of all the town from above (on clear days you will see the alps and the Monte Bianco easily)
2) From the Duomo square, heading NW you will go to piazza Mercanti, with its famous loggia, and then to piazza Cordusio, which has 2 interesting buildings, the Post and the Unicredito buildings, all built in the 19th century. Then walking along via Dante you will reach Largo Cairoli and then a bit further Piazza Castello and the famous Castello Sforzesco, a real large castle, which was rebuilt after WW2 and is the original castle where the rulers of Milan used to live in the renaissance period.
3) Behind Castello Sforzesco is the Parco Sempione, one of the nicest parks of Milan, very well kept and very relaxing. In summer the famous Bar Bianco hosts very nice "aperitivi" in the evenings, with music and drinks and all the "bella gente" sitting outside and checking out each other. There's 2 other famous night clubs/restaurants in the park, one is the Old Fashion, in via Alemagna, one is the Just Cavalli Cafè, very near to it. Both are pretty trendy and crowded in the evenings, particularly in summer.
4)In the Parco Sempione there is the Museo della Triennale, wich is a famous design museum with all the famous design pieces that were invented in Milan (probably you don't know it but several things which you have in your house/office were invented here, from lamps to tables to chairs).
5) If from LArgo Cairoli rather than go straight you turn right into Foro Buonaparte, you will then head towards Brera, the most charming area of Milan with a number of nice shops and bars and restaurants. Places to see are Piazza del Carmine, via Fiori Chiari, and then you will reach the Pinacoteca di Brera, which has a huge number of famous paintings from the 14th century onwards, including Caravaggios and many others
6) From Pinacoteca di Brera, walking along via Brera and via Verdi you will reach Piazza Scala, where the famous theatre is. Tickets are usually sold out but if you are prepared to pay a premium your hotel will probably find them for you.
7) From Piazza Scala you will see a big building with a gallery, that's the Galleria Vittorio Emanuele, built in the 19th century and something to see, with its famous coffee bars and restaurants and its glass ceiling. At the end of Galleria Vittorio Emanuele you will be again in Piazza Duomo.
8) If you are still not tired, from Duomo you can walk again to Piazza Cordusio, and then take Via Meravigli, at the end of via Meravigli you will find the famous Pasticceria Marchesi, which makes the best Panettone of Milan and is something to be tried once. Past Marchesi, walk along Corso Magenta and at one point you will reach Santa Maria delle Grazie, a very nice church. In it you will be able to see the famous painting by Leonardo da Vinci: the last supper. You have to book tickets ahead or you won't be able to see it unless you contact one of the many tour vendors that can pop you on a half-day tour sometimes at the last minute.
9) Walk along corso Magenta, you will arrive in Piazzale Baracca, cross it and then you will be in Corso Vercelli, a street with a number of nice shops where Milanese do their shopping (while the shops in via Montenapoleone and via Spiga are mainly for rich tourists).