Simple regression means regression with a single right-hand side variable, as in y = a + b x + u. Multivariate regression means regression with multiple right-hand side variables, as in y = a + b1 x1 + ... + bn xn + u. This distinction is not related to your problem (the right-hand side variable being endogenous) and it will not solve your problem.
You can read more on the subject by clicking on the following links:
http://en.wikipedia.org/wiki/Linear_regression
http://en.wikipedia.org/wiki/Regression_analysis
When you're reading either article, you can click on any of the embedded links (in the text of the article) to jump to related subjects.
Let's take it one step at a time:
1. Find a set of non-random variables that you think would correlate with the temp. at site #2, and match these with the measurements at site #2. Knowing very little about the subject, I can think of the following variables: time of the day of the measurement, day of the year of the measurement, the season of the measurement, the year of the measurement, altitude of the measurement. Each of the variables should have more than one value, that is, it cannot be constant across all measurements. (For example, if all measurements are taken at an identical altitude then "altitude" may not be in the list.) You may have a longer and/or a better list. Do you understand/can you do this?
2. Regress the measured temperature at site #2 on those variables. Do you understand/can you do this?
3. Save the "predicted values" from that regression. (Alternatively, save the residuals, then take the difference "measured temp. - residual" for each observation, which will give you the predicted temp.) Do you understand/can you do this?
4. Regress the measured temp. at site #1 on the predicted values that you obtained in the previous step. Do you understand/can you do this?
Please go over the steps above. Let me know any point on which you need specific explanations. The narrower and more specific your questions, the better I can be of help.