Some areas have been or are being developed for tourism; there you can expect to find some modern amenities, Western food, English speakers and (by Chinese standards) high prices. Once you get out of those areas, expect none of the above.
On the overnight buses, you have to remove your shoes when boarding and put them back on to get off for food and restroom stops. You may want to buy a pair of "kung fu" slippers (15 to 20 RMB) to make this easier, even if you normally travel in boots or laced shoes.
The two end points, Kunming and Hong Kong, both have good air links to various places. See their articles and Discount airlines in Asia for details. Both also have rail connections to the rest of China.
From Kunming, the most interesting route is to travel either by train or bus into Guizhou, a relatively poor and non-touristic province with many ethnic minorities, then by bus through less traveled country to Guilin. This article treats that as the main route. Various other possibilities are under "alternate routes" below.
Anshun is a moderately interesting town and the hub of Western Guizhou. China's biggest waterfall is nearby and there are also a number of caves in the area.
The overnight Kunming-Anshun bus is not recommended; it is at least 16 hours and neither clean nor comfortable. Take the train or break up the journey with an intermediate stop, perhaps at Qujing in Eastern Yunnan or Pan Xian in Western Guizhou.
From Anshun, it is a couple of hours by bus to Guiyang, the provincial capital. This is not a particularly interesting town, but might be worth looking around. A possible side trip would be to go a few hours north from Guiyang to Zunyi. This is an important site for Chinese Communist history and the scene of the Zunyi Conference during the Long March.
From Guiyang, it is about four hours by bus to Kaili, a trading town with many interesting villages nearby. This is the hub of Eastern Guizhou, probably the most interesting place on this route.
Alternately, you could take a train to Kaili from Guiyang or even directly from Kunming. Trying to get the train from Anshun is not recommended; it is hard to get seats except at major stations.
The first step is to get to Congjiang, a fairly uninteresting place in the South of Guizhou. There is a direct Kaili-Conjiang bus, eight hours through interesting scenery.
An alternate route, slower but likely more interesting, would be Kaili-Sansui-Jinping-Liping-Conjiang on a series of buses.
From Conjiang, two more buses get you to Guilin:
Sanjiang is worth a stop. It is the capital of a Dong minority area and has some sites and shopping.
Longsheng, between Sanjiang and Guilin, has the famously scenic "Dragon's Backbone" rice terraces. If you haven't already seen more than enough terraced fields in Guizhou, you might stop for these.
For most Western tourists, the main reason for going to Guilin is to get to Yangshuo, an hour and a bit south by bus. However, Guilin itself might be worth a stop. Certainly it is very popular with Chinese tour groups.
Either way, you can reach Hong Kong.
Probably the most interesting route would be:
The fastest route is an overnight bus to Shenzhen, right across the border from Hong Kong.
From Kunming, you can take a train through sensational mountain scenery to Nanning, the capital of Guangxi. From Nanning, it is a short trip by bus or train to tourist center Guilin. See above for routes from Guilin to Hong Kong.
There are also flights possible to both Nanning and Guilin from most major cities in China.
The fastest reasonably priced way from Kunming to Hong Kong or vice versa is by a plane/ferry combination, about 4 hours / 850+ RMB. You could fly directly to Hong Kong, but it is usually significantly cheaper to land in Shenzhen and take a ferry.
Many foreigners in China need to get a new visa every six or 12 months and Hong Kong or Macau are good places for this. For most passports you can get a multiple entry business visa with just a photo and money. The plane/ferry combination is the usual method for such "visa runs".
''Kunming - Hong Kong''
''Hong Kong''
A convenient way to book the ferry and plane ticket together is at the [http://www.ctshk.com/english/index.htm China Travel Service (HK)]. It is easy to find as it is directly opposite [http://en.wikipedia.org/wiki/Chungking_Mansions Chunking Mansions] in Kowloon where many backpackers stay.
[http://www.turbojetseaexpress.com.hk/e/sailing_schedule_fare_table.asp?vname=sailing_schedule_fare_table Turbojet Ferry Schedule]
Armed robbery is rare, but has been reported. Victims are generally lone travelers, often female. Try to stay in a group, especially on treks through isolated areas.
Altitude sickness is a risk in some areas, especially if you go west of Kunming up toward the Himalayas.
Both cities are also well connected to the Chinese rail network. From Kunming, the possibilities are: